TWI626987B - Integrated gas turbine and conversion system process - Google Patents

Abstract

The system disclosed by an integrated approach and system to generate power converter and the non-cyclic C ₅ to feed non-aromatic cyclic C ₅ hydrocarbons. A combustion apparatus such as a turbine, and a reactor tube containing a catalyst compound are disclosed. Also discloses a process involving the non-cyclic C ₅ feed and contacting the catalyst composition obtained cyclic C ₅ hydrocarbons and a method.

Description

Integrated gas turbine and conversion system method [Related application cross-reference]

The present invention claims the priority and benefit of USSN 62/250,674, filed on Nov. 4, 2015, and European Patent Application No. 16153715.4, filed on Feb. 2, 2016.

The present invention relates to integrated gas turbine and the tubular reactor is heated by convection and the sum of the power generating method to be non-cyclic C ₅ feed conversion comprising use of a cyclic compound of ₅ C product in.

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, synthetic rubbers). , solvents, fuels, fuel additives, etc.). Cyclopentadiene (CPD) is today a small by-product of vapor-cracking of liquid feeds, such as naphtha and heavier feeds. As existing and new steam cracking facilities switch to lighter feeds and less CPD is manufactured, the demand for CPD is increasing. The high cost due to supply constraints affects the potential of CPD in the polymer. 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 desirable. 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.

Advantageously, the catalyst system is to be able to use a C-rich starting material for producing C ₅ cyclic compound ₅ (which includes, as the major product of CPD), to produce CPD, while the light (C4-) for producing the byproduct minimized. 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 the conversion are improved, the unsaturated material is more expensive than the saturated feedstock. Since the chemical reactions and straight-chain C ₅ lower branched C ₅ relative value (difference due octane) both, straight-chain C ₅ superior backbone structure a branched C ₅ persons. 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 bio-feeds.

Today the use of various 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 "Development of Dehydrogenation Catalysts and Processes," Topics in Catalysis, vol. 55, pp. 1297-1308, BVVora, Catalysis, Vol. 55, pp. 1297-1308, 2012. And JC Bricker, "Advanced Catalytic Dehydrogenation Technologies for Production of Olefins," Topics in Catalysis, vol. 55, Vol. 55, pp. 1309-1314, Catalysis, 2012. 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 this catalyst has poor selectivity and productivity to 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. The cyclization of C ₆ and C ₇ alkanes occurs by means of the formation of an aromatic ring, which does not occur in C ₅ cyclization. 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 material, and C ₆₊ both cyclized to form an aromatic C ₆ ring, will require different catalysts to the conversion of non-cyclic C ₅ to C ₅ cyclic.

Ga-containing ZSM-5 catalysts are used in a process to produce 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 Conversion Using Mechanically Mixed Catalysts of Ga ₂ O ₃ /H-ZSM-5" C8 aromatics and n-pentane over Ga ₂ O ₃ /H-ZSM-5 mechanically mixed catalysts," Catalysis Letters, vol. 9, pp. 35-42. No production of cyclic C _{5 was} reported, but at 440 ° C And 6 wt% or more of aromatics at 1.8 hr ^-1 WHSV. It has also been shown that Mo/ZSM-5 catalyst dehydrogenates and/or cyclizes alkanes (especially methane). See Y.Xu, S. Liu, X.Guo, L. Wang, and M.Xie, Activ. 30, pp. 135-149, 1994, "Using Mo/HZSM-5 Zeolite Catalyst to Activate Methane Without Oxide"("Methaneactivation" 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 cyclic C manufactured and ₅ of a high yield of cracked products which show: in a ZSM-5 catalyst to sediment the alkanes may be converted to C ₆ cycloalkyl, C ₅ ring manufacture but need not be.

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) deals with similar chemistry but utilizes tin-containing crystalline microporous materials. As with the NU-87 catalyst, only the C5 dehydrogenation was shown to produce 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 subsequently 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 approach inadequate. In addition, 1,3-pentadiene is not an easily available raw material, unlike n-pentane. See also Kennedy et al., Industrial and Engineering Chemistry, 1950, pp. 547-552, "Formation of Cyclopentadiene from 1,3-Pentadiene," Industial And Engineering Chemistry, vol. 42, pp. 547-552, 1950).

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 for conversion to CPD using 2% Pt/SiO ₂ , 1,3-pentadiene, n-pentene, and n-pentane at 600 ° C were generally higher than 53%, 35%, and 21%, respectively. While observing the initial manufacture of CPD, sharp passivation of the catalyst was observed within a few minutes before the reaction. Using Silica Pt-containing experiments showed that of the PRC using moderate conversion Pt-Sn / SiO ₂ of n-pentane, but the selectivity and yield of the C ₅ cyclic poor 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,") MSUniversity of Central Florida, 1977 was presented. Marcinkowski showed a conversion of 80% 1,3-pentadiene with H ₂ S at 80 ° C and a CPD conversion of 80%. The high temperature, limited feedstock, and the possibility of sulfur-containing products, which subsequently require 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. In HZSM-5, HBEA and SAPL-11, " Catalysis Letters , vol. 122, pp. 267-273, 2008", the reaction of n-butane was studied using a Pt-containing zeolite comprising H-ZSM-5. At temperatures (250-400 ° C), he reported the use of the Pt-zeolite to efficiently hydroisomerize n-pentane, but did not discuss the formation of cyclopentene. I want to avoid this harmful chemistry because of the branched C5 The cyclic C ₅ is not as efficiently produced as the linear C5, as discussed above.

Li et al., in the Catalysis Journal, Vol. 255, pp. 134-137, "Catalytic dehydroisomerization of n-alkanes to isoalkenes," Journal of Catalysis , vol. Dehydrogenation of n-pentane containing Pt zeolite has also been studied in 255, pp. 134-137, 2008), in which 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 C2-C5 alkanes to obtain corresponding olefins. Similarly, US 2,982,798 discloses a process for the dehydrogenation of aliphatic hydrocarbons containing from 3 to 6 (inclusive) 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. 7,536,863 describes a combined cycle in which a portion of the gas turbine exhaust stream is recirculated to the gas turbine and the remaining gas turbine exhaust stream is discharged from the cycle.

In addition, there are many challenges in designing an on-purpose CPD manufacturing method. For example, the C ₅ hydrocarbons to the reaction is extremely endothermic CPD 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 objective is to cyclopentadiene, its manufacture in the aging properties unduly C _4- lysate and have acceptable catalyst, cyclopentyl generated by the C ₅ rich material in high yield Diene. 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. There is also an integrated method and reactor system that requires efficiency to produce power and intentional CPD.

The present invention relates to a method of converting a non-cyclic C ₅ C ₅ hydrocarbons to cyclic hydrocarbons (including, but not limited to, cyclopentadiene ( "CPD")), wherein the method comprises: a) compressing the oxygen-containing gas stream; b) the compressed gas stream to oxidize the fuel to produce hot gas stream; c) providing a feedstock comprising acyclic hydrocarbons of the C _5; D) such that the feedstock with a catalyst composition in a reaction tube in parallel, by simultaneously convection heat from the hot gas stream to the outer surface of the reactor wall; and e) to obtain a reaction effluent comprising C ₅ hydrocarbons of cyclic, wherein the cyclic hydrocarbon comprises a C ₅ cyclopentadiene.

Preferably, the oxidation of b) can be carried out in a turbine, a fuel cell, a furnace, a boiler, an excess air burner, a fluidized bed, and/or other known combustion devices. The fuel can be a solid (e.g., coal), a liquid (e.g., fuel oil), a gas (e.g., H2, methane, natural gas, etc.), or a mixture thereof.

The present invention also relates to a power generation and the non-cyclic C ₅ hydrocarbons method of converting cyclic C ₅ hydrocarbons, wherein the method comprises: a) compressing the gas stream containing oxygen; b) to the compressed combustion air in the turbine fuel gas to generate a power turbine and turbine exhaust stream; c) providing a raw material of the non-cyclic C ₅ hydrocarbons comprising; D) of the feed with the catalyst composition in a reaction tube in parallel, while the heat by convection from the turbine exhaust gas stream to the outer surface of the reactor wall; and e) obtain effluent comprising C ₅ cyclic hydrocarbon of the reactor, wherein the hydrocarbon comprises a cyclic C ₅ cyclopentadiene.

The present invention relates to an electric power generated by the convection heating of the reactor and converting the non-cyclic C ₅ C ₅ hydrocarbons to cyclic hydrocarbons, wherein the method comprises: a) compressing the gas stream containing oxygen; b) in the fuel cell to the compressed air fuel combustion gas stream to generate electricity and heat; c) providing a raw material of the non-cyclic C ₅ hydrocarbons comprising; D) of the feed with the catalyst composition in a reaction tube in parallel while by convection heat from the hot gas stream to the outer surface of the reactor wall; and e) obtain effluent comprising C ₅ cyclic hydrocarbon of the reactor, wherein the hydrocarbon comprises a cyclic C ₅ cyclopentadiene.

The present invention also relates to a convection heating produced by the reactor and the vapor integrated method to convert the non-cyclic C ₅ C ₅ hydrocarbons to cyclic hydrocarbons, wherein the method comprises: a) compressing the gas stream containing oxygen; b) in a boiler fuel to the oxidation of the fuel gas stream to produce a vapor and a hot gas stream; c) providing a raw material of the non-cyclic C ₅ hydrocarbons comprising; D) such that the feedstock with a catalyst composition in a reaction tube in parallel while by convection heat from the hot gas stream to the outer surface of the reactor wall; and e) obtain effluent comprising C ₅ cyclic hydrocarbon of the reactor, wherein the hydrocarbon comprises a cyclic C ₅ cyclopentadiene.

In one aspect of the invention, the reactor tube has an inverse temperature distribution. In another aspect of the invention, the reactor tube has an isothermal or substantially isothermal temperature profile.

In another aspect of the invention, the feedstock and the hot gas stream, such as the turbine exhaust stream, flow in the same direction to provide a heat flux near the inlet that is greater than a heat flux near the outlet of the reactor tube the amount.

Still in another aspect of the invention, the use of a turbine The machine power is i) rotating the generator to generate electricity and/or ii) rotating the compressor.

Still another aspect of the invention comprises i) providing two or more parallel reactor tube bundles, the reactor tube comprising a catalyst composition and ii) providing a reactivation gas or a regeneration gas to one or more reactor tubes and simultaneously comprises a non-cyclic C ₅ hydrocarbons of the feed to provide one or more different tube bundle reactors.

There is one aspect of the present invention relates to a system and the non-power generation converting hydrocarbon cyclic C ₅ to C ₅ hydrocarbon ring system, wherein the integrated switching system comprising: a) a compressor for compressing the oxygen gas stream comprising b) a tank for burning fuel in the compressed gas stream to produce a hot gas stream in the combustion apparatus; c) a feed stream comprising acyclic C ₅ hydrocarbons; d) a parallel reactor tube comprising a catalyst composition ; and e) produced by following the C ₅ hydrocarbon comprises a cyclic reactor effluent stream: the feedstock is contacted with the catalyst composition in at least a portion of the (other) parallel reactor tube, while by convection the heat from the hot gas stream delivered to the outside wall surface of the reactor, wherein the hydrocarbon comprises a cyclic C ₅ cyclopentadiene.

Preferably, the tank is a turbine, a fuel cell, a furnace, a boiler, an excess gas burner, a fluidized bed, and/or other known combustion devices.

There is one aspect of the present invention relates to a system and the non-power generation converting hydrocarbon cyclic C ₅ to C ₅ cyclic hydrocarbons integrated switching system, wherein the integrated switching system comprising: a) a compressor for compressing comprising oxygen of the gas stream; b) a turbine for the turbine to the compressed gas stream combusting fuel gas to produce turbine power and a turbine exhaust stream; c) a feedstream comprising a non-cyclic C ₅ to hydrocarbon; D) comprising contact parallel reactors composition of the medium pipe; and e) produced by following the C ₅ hydrocarbon comprises a cyclic reactor effluent stream: the feedstock with the catalyst in the at least a portion (s) of parallel reactor tubes contacting the composition, while the convection by the turbine exhaust stream to transfer heat to the outside wall surface of the reactor, wherein the hydrocarbon comprises a cyclic C ₅ cyclopentadiene.

Another aspect of the invention comprises: a) a reactivation gas stream comprising H2; and b) a coke material for contacting the reactivation gas with the catalyst composition to remove at least a portion of the catalyst composition s installation.

Still another aspect of the invention comprises: a) a purge stream comprising an inert gas and a regeneration gas stream comprising a material for oxidation; and b) means for: i) driving any combustible fuel from the reactor tubes The gas, including the feedstock and reactor product, and ii) contacting the regeneration gas with the catalyst composition to remove at least a portion of the coke material on the catalyst composition by oxidation.

10‧‧‧Materials

11‧‧‧ catheter

12‧‧‧Switch

13‧‧‧ catheter

14‧‧‧Inlet manifold

15‧‧‧ catheter

16‧‧‧Reactor inlet

20‧‧‧Blocking

23‧‧‧Parallel reactor tubes

26‧‧‧ catheter

32‧‧‧Reactor effluent

40‧‧‧Resurrection system

41‧‧‧Revitalizing gas

42‧‧‧Switch

43,44‧‧‧ catheter

45‧‧‧Revitalizing gas

50‧‧‧Regeneration system

51,52‧‧‧ catheter

53‧‧‧Renewable gas

54‧‧‧ Driving gas

60‧‧‧ airflow

61‧‧‧Compressor

62‧‧‧fuel gas

63‧‧‧ turbine

64‧‧‧ turbine power

70‧‧‧ Turbine exhaust flow

71‧‧‧ catheter

72‧‧‧ cooled exhaust gas stream

80‧‧‧Block

81‧‧‧Additional combustion device

82‧‧‧Additional fuel gas

90‧‧‧Vapor

91‧‧‧Switch

92‧‧‧ catheter

100‧‧‧ filter

101‧‧‧Transition system

105‧‧‧Compressor

110‧‧‧ turbine

116‧‧‧Baffle

120‧‧‧burning device

121‧‧‧Pipe Burner

130‧‧‧Inlet manifold

131‧‧‧reactor tube

132‧‧‧Export manifold

140‧‧‧heat transfer device

141‧‧‧Renewable gas

142‧‧‧ catheter

150‧‧‧ bypass chimney

151‧‧‧Muffler

152‧‧‧ chimney

153‧‧‧Exhaust muffler

160‧‧‧Generator

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‧‧‧reactor

214, 215, 216, 217‧ ‧ catheter

Figure 1 depicts the configuration for a multiple reactor.

Figure 2 depicts a diagram of a conversion system and method.

Figure 3 depicts an integrated conversion system and method.

4 depicts the overall carbon yield in the example 3, cyclic C ₅ hydrocarbons in the relative time (TOS) on the stream, while maintaining an inverse temperature profile (6 inches up to 500 deg.] C after 600 ℃), or isothermal temperature profile (the 6吋 is 600°C from head to tail).

5 depicts the overall carbon yield in Example 3 C ₁ -C ₄ hydrocarbons relative TOS, while maintaining an inverse temperature profile (6 inches up to 500 deg.] C after 600 ℃), or isothermal temperature profile (6 inches from start to finish are the 600 ° C).

FIG 6 depicts in Example 5, in an oil continuous reactor operation strategy and intermittent H ₂ resurrection reactor operation strategy, cyclic C5 hydrocarbons of address - time - yield (STY) (i.e. the cC5 Mohr / Pt Mo / sec) relative TOS.

definition

For the purposes of this specification and the accompanying claims, many words 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) 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 reduce it by 10% or by 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 a Dimes-Alder reaction over a wide 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 (PNAs) including naphthalene, anthracene, Benzophenanthrene, and its alkylation variant). 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 aromatics (PNAs) 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, It is adsorbed on 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 "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.

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).

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. Wait.

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 two or more of them. mixture.

The term "Group 1 alkali metal" means an element in Group 1 of the Periodic Table and includes, but is 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 mixtures of two or more thereof.

The term "constraint index" is defined in US Pat. No. 3,972,832 and US Pat. No. 4,016,218, the disclosure of which is incorporated herein by reference.

As used herein, the term "MCM-22-based 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 having a MWW framework phase. (The unit cell is a spatial arrangement of atoms, and if it is laid out in a three-dimensional space, the crystal structure is described. These crystal structures were in the fifth edition of the 2001 Atlas of Zeolite Framework Types. Discussion, the entire content of which is incorporated by 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 (more a single layer of 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 unit crystal The layer thickness is formed by stacking, compressing, or combining at least two single layers having a unit lattice thickness. The stack of such second building blocks may be in a regular manner, an irregular manner, a random manner, or any combination thereof; and a molecular sieve, which is any rule or random 2 by a unit lattice having a phase of the MWW architecture. Made of dimensional or 3-dimensional combination.

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 "carbon selectivity of at least 30% of the C ₅ cyclic" means: pentane in the transformed mole of carbon per 100 mole of carbon 30 is formed in the C ₅ ring.

As used herein, the term "conversion" means the molar number of carbon in the product is converted to the non-cyclic C ₅ feedstock. The term "at least 70% of the non-cyclic C ₅ to become the conversion rate of the raw product" is meant at least 70 mole% of the non-cyclic C ₅ feed is converted to product.

As used herein, the term "reactor system" refers to a package. A system comprising one or more reactors and all required 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 a defined reactor and a reaction zone within a single reactor apparatus and, if applicable, a reaction zone that passes 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 reactor effluent are considered to comprise the effluent from the first reaction zone of the single reactor and the effluent from the second reaction zone, respectively.

For the purposes of the present invention, 1 psi is equal to 6.895 kPa. In particular, 1 psia is equal to 1 kPa absolute (kPa-a). Similarly, 1 psig is equal to 6.859 kPa gauge (kPa-g).

The present invention relates to a non-cyclic C ₅ hydrocarbon conversion to C ₅ hydrocarbon cyclic process. In certain aspects, the invention relates to a power generation method and the non-conversion integrated hydrocarbon cyclic C ₅ to C ₅ cyclic hydrocarbons, wherein the method comprises: compressing the gas stream containing oxygen; in the turbine to the the compressed gas stream to produce a fuel gas combustion turbine and a power turbine exhaust stream; providing a raw material of a non-cyclic C ₅ hydrocarbons; the feedstock and the catalyst composition is contacted in reactor tubes in parallel, while the heat by convection from the turbine exhaust gas stream to an outer wall surface of the reactor; and the reactor effluent is obtained comprising a cyclic hydrocarbon of C _5, C ₅ wherein the cyclic hydrocarbon comprises cyclopentadiene. Various aspects of the conversion system and method enable maintaining an inverse temperature profile in the reactor tube, which can advantageously minimize the formation of carbonaceous materials and enhance product yield. Other aspects of the present invention allows an operator to sample the reactor outlet at a pressure below the atmospheric pressure to form a cyclic C ₅ to strengthen the product. Still other aspects of the present invention present the advantages of improved overall energy utilization and minimization of energy costs by extracting the highest value of heat as a shaft work while reducing or eliminating the need to heat the conversion process. The number of additional combustion devices (eg, burners).

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 steam cracking) for producing the lysed C ₅ (different degree of unsaturation: alkenes, dienes, alkynes).

In one or more aspects of the example, useful in the methods of the present invention, non-cyclic C ₅ feed comprising pentane, pentene, pentadiene, and mixtures of two or more. Preferably, in one or more of the example aspects, 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 such as benzene, preferably the C ₆₊ aromatic compound is present in an amount of less than 5 wt%, preferably less than 1 wt%, preferably less than 0.01 Wt%, 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) in the co-feed is also fed into the first reactor. Preferably, at least a portion of the hydrogen co-feed material blended with the C ₅ prior to feeding 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.

The second aspect of the present invention is also a kind of 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 aspects instances, the conversion product of the process of the non-cyclic C ₅ feed comprising C ₅ cyclic compound. The cyclic C ₅ compound comprises one or more of cyclopentane, cyclopentene, cyclopentadiene, and a mixture thereof. In one or more aspects instances, the C ₅ cyclic compound comprises at least about 20wt%, or from about 30wt%, or from about 40wt%, or from about 50wt% of cyclopentadiene, or from about 10wt% to about 80wt %, optionally in the range of 10 wt% to 80 wt%.

In one or more aspects instances, the non-cyclic C ₅ conversion conditions include a temperature of at least, the outlet pressure of the reactor, the reactor pressure drop and the weight hourly space velocity (WHSV). The temperature is in the range of from about 450 ° C to about 800 ° C, or in the range of 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 (reactor inlet pressure - reactor outlet pressure) measured from the reactor inlet to the reactor outlet 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 about 5 to about 45 psi. The weight hourly space velocity 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) no matter comprising hydrogen, C ₁ -C ₄ hydrocarbons, or both, or not, 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 exemplary aspects, the present invention is directed to a method of converting n-pentane to cyclopentadiene comprising the steps of: reactor outlet temperature of from 550 ° C to 650 ° C, from 4 to about 20 psia. The reactor outlet pressure, a reactor pressure drop of from about 5 to about 45 psi, and an hourly weight space velocity of from 2 to about 20 hr ^{-1 to} give n-pentane and optionally hydrogen (if present, generally H ₂ to n-pentane The alkane is present in a ratio of from 0.01 to 3.0 in contact with one or more catalyst compositions including, but not limited to, the catalyst compositions described herein to form cyclopentadiene.

Catalyst composition

Catalyst compositions useful herein include microporous crystalline metal silicates such as crystalline aluminosilicates, crystalline ferric silicates, or other metal-containing crystalline silicates such as those metals or The metal-containing 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 series materials), wherein one or more metals of Groups 8, 11 and 13 of the Periodic Table of the Elements (preferably Fe, Cu, Ag, Au, B, Al, Ga, and/or In) One or more) are incorporated into the crystal structure during the synthesis or are impregnated after crystallization. It is recognized that metal phthalates may have one or more metals present and, for example, one material may be referred to as ferrite, but most likely still contain 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. In this article The aluminosilicates 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. A group consisting of a mixture of EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30, and 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) 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 a mixture 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 example aspects, the crystalline metal citrate has a Si/M molar ratio (wherein M is a Group 8, 11 or 13 metal) 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 example aspects, 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 aspect of the invention, the microporous crystalline metal ruthenate (such as aluminosilicate) is associated with 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 example aspects, the Group 10 metal includes or is selected from the group consisting of Ni, Pd, and Pt, preferably Pt. The catalyst The Group 10 metal content of the composition is at least 0.005 wt% based on the weight of the catalyst composition. In one or more example aspects, 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%, based on the weight of the catalyst composition. In the scope.

In one or more example aspects, 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.

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

In one or more example aspects, 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 mixtures of two or more thereof. . In one or more example aspects, 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 example aspects, 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 mixtures of two or more thereof. 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 a mixture of two or more thereof.

In one or more example aspects, 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 example aspects, the 11th group content is The weight of the catalyst composition is in the range of from about 0.005 wt% to 10 wt%, or from about 0.005 wt% to about 1.5 wt%.

In one or more example aspects, 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. . The alpha value is as described in US 3,354,078; The Journal of Catalysis, Vol. 4, p. 527 (1965); p. 6, p. 278 (1966); and 61, 395 (1980), used. The fixed temperature of 538 ° C and the variable flow rate detailed in the Journal of Catalysis, Vol. 61, page 395, were determined.

In one or more example aspects of the aluminosilicate, the molar ratio of the Group 1 alkali metal to Al is at least about 0.5, or from at least about 0.5 to about 3, preferably at least about 1, more preferably at least About 2.

In one or more exemplary aspects of the aluminosilicate, the molar ratio of the Group 2 alkaline earth metal to Al is at least about 0.5, or from at least about 0.5 to about 3, preferably at least about 1, more preferably at least About 2.

In one or more example aspects, the molar ratio of the Group 11 metal to Group 10 metal is at least about 0.1, or from at least about 0.1 to about 10, preferably at least about 0.5, more preferably at least about 1. In one or more example aspects, 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 instances aspect, the non-cyclic C ₅ at conversion conditions (raw material containing n-pentane and of equimolar H _2, at a temperature range of from about 550 deg.] C to about 600 deg.] C in the at 10psia 3 The use of the catalyst composition of the present invention provides at least about 70%, or at least about 75%, or the n-pentane partial pressure between, and an hourly weight space velocity of n-pentane of 10 to 20 hr ^-1 . 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 instances aspect, the non-cyclic C ₅ at conversion conditions (which include n-pentane feed with equimolar H _2, at a temperature range of from about 550 to about 600 deg.] C in deg.] C, 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 of 10 to 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 instances aspect, the non-cyclic C ₅ at conversion conditions (which include n-pentane feed with equimolar H _2, at a temperature range of from about 550 to about 600 deg.] C in deg.] C, 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 of 10 to 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 wear and more resistant to the harsh conditions that would be exposed during use of the hydrocarbon conversion application. 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% by weight, and more often, especially The composite is prepared in the form of beads, extrudates, pellets, oil droplet-forming particles, spray dried particles, and the like in an amount of from about 2 to about 80% by weight of the composite.

The shape and design of the catalyst composition is preferably configured to minimize pressure drop, increase heat transfer, and minimize mass transfer 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.

Suitable catalyst shapes and designs 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 cross-section of the catalyst composition is shaped to have one or more leaves and/or concavities. Further, the leaves and/or concave surfaces of the catalyst composition are spiraled. The catalyst composition may be an extrudate having a diameter of from 2 mm to 20 mm (eg, from 2 mm to 10 mm, or from 5 mm to 15 mm); and the cross-section of the catalyst composition may be shaped to have one or more leaves and/or concavities; The leaves and/or concave surfaces of the catalyst composition are helical. Particle shapes for fixed bed reactors (combustion tubes, convection tubes, and circulation), vane, concave, spiral, etc. are particularly useful, and for fluid bed reactors, 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 may be shaped to have one or more leaves and/or concavities; and the leaves and/or concavities of the catalyst composition are helical. Shapes may also include holes or perforations in the shape to increase voidage and improve quality 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 formed inorganic support structures may also include ceramic or metal bubbles and 3D printed structures. The coating of the active catalyst 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; most preferably 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, and thus, the catalyst composition loses some 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), and a Group 10 metal (such as Pt) and a Group 1 alkali metal (such as sodium or potassium); 3) a crystalline aluminosilicate (such as ferric or iron-treated ZSM-5), which is a Group 10 metal (such as Pt) and a group 1 alkali metal (such as sodium or potassium) combination; 4) crystalline aluminosilicate (zeolite L), which is related to Group 10 metals (such as Pt) and Group 1 alkali metals (such as potassium) Binding; 5) crystalline aluminosilicate (such as ZSM-5) in combination 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 first Alkaloid metal ruthenates (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 baic acid) The salt is modified, preferably potassium citrate, sodium citrate, calcium citrate and/or magnesium citrate, preferably potassium citrate and/or sodium citrate. The Group 10 metal of the catalyst composition is present in an amount of at least 0.005% by weight based on the weight of the catalyst composition, preferably from about 0.005 wt% to about 10 wt%, based on the weight of the catalyst composition, or It is in the range of from about 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 trademarks DAVISIL 646 (Sigma Aldrich), Davison 952, DAVISON 948 or Davison 955 (Davison Chemical Division of WR Grace and Company).

In different ways, the catalyst material (and random matrix material) The average diameter of the material may be from about 5 μm to about 50 mm, such as from about 25 μm to about 3500 μm. Preferably, the catalyst material (and optional matrix or binder) may have an average diameter of 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 30 μm to about 400 μm, more preferably from about 40 μm to about 300 μm.

The "average diameter" for particles in the range of 1 to 3500 [mu]m was determined using a Mastersizer ^(TM) 3000 available from Malvern Instruments, Ltd., Worcestershire, England. Unless otherwise stated, the particle size is determined at D50. D50 is the particle diameter value at a point of 50% 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% is less than 5.8 μm.) For the "average diameter" of particles in the range of 3 mm to 50 mm Microdevices were measured on representative samples of 100 particles.

For more 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), November 4, 2015 USSN 62/250,688, filed on November 4, 2015; 4) USSN 62/250,695, filed on November 4, 2015; and 5) USSN 62/250,689, dated November 4, 2015; Incorporated herein.

Conversion system

The feedstock is fed to the conversion system comprising parallel reactor tubes positioned within the enclosure. Optionally, the feedstock is fed to the adiabatic pilot reaction zone before being fed to the parallel reactor tubes. 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 reactor tube configuration or enclosure can be used, preferably, the conversion system includes a plurality of parallel reactor tubes within the convective heat transfer enclosure. Preferably, the reactor tube is straight, rather than having a coiled or curved path through the enclosure (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, reducing the cross-sectional dimensions of the tubes increases the number of tubes for a particular production rate. Therefore, the selection of the optimum tube size is preferably to minimize the cross-section temperature gradient and minimize the construction cost. A suitable cross-sectional dimension (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 a stream of hot gases generated by oxidizing the fuel with a compressed gas stream comprising oxygen. Often, the tubes are heated with a turbine exhaust stream produced by burning a fuel gas with a compressed gas turbine containing oxygen. In other aspects, the reactor tube is heated by convection by hot gas generated by combustion in any known combustion apparatus, wherein the combustion apparatus is preferably selected from the group consisting of a fuel cell, a furnace, a boiler, or an excess Air burner. However, it may be preferable to heat the reactor tube with turbine exhaust, as well as other advantages, as well as the co-generation of power or shaft work.

The compressed gas system comprising oxygen is compressed in at least one compressor. Preferably, the compressed gas is compressed air. Optionally, the compressed air contains oxygen enriched air by partial separation of nitrogen. Any compressor and/or turbine known in the art can be used. Examples of compressors and turbines suitable for use in such a conversion system are described in US 7,536,863, which is incorporated herein by reference. Preferably, the turbine additionally generates power. The turbine power can be used to rotate a compressor that compresses the compressed air containing oxygen. Optionally, the conversion system additionally includes a generator and/or another compressor that is rotated by the power generated by the turbine. The generator can generate electricity.

By convection, heat is transferred from the hot gas stream (often the turbine exhaust stream) to the outer surface of the reactor tube wall. The reactor tube can be positioned within the enclosure in any configuration. Preferably, the reactor tube is positioned within the enclosure to flow the feedstock and the hot gas stream in the same direction. The co-flow provides a heat flux near the inlet of the reactor tube that is greater than the heat flux near the outlet of the reactor. Higher heat is required near the inlet of the reactor tube, such as the heat required to provide the heat of reaction and to heat the feed to the desired reaction temperature. What is desired is a lower heat flux (the amount of heat flux relative to the pressure inlet) in the vicinity of the outlet portion of the reactor tube to avoid higher than desired temperature, for example to promote undesired coking And/or the temperature at which the coking and/or cracking occurs for a particular catalyst, operating pressure, and/or residence time as the temperature is above the temperature range of the conversion conditions.

The conversion system optionally additionally includes at least one combustion device that inputs additional thermal energy into the hot gas stream (such as the turbine exhaust stream). Additional heat may be provided to the hot gas stream (e.g., the turbine exhaust stream) upstream or downstream of the reactor tube by a combustion unit. Further fuel gas may be combusted with unreacted oxygen in the hot gas stream (e.g., the turbine exhaust stream) to transfer heat from the hot gas stream (e.g., the turbine exhaust stream) to the reactor tube wall prior to convection from the hot gas stream (e.g., the turbine exhaust stream) Or afterwards, the temperature of the hot gas stream (e.g., the turbine exhaust stream) is increased. The additional heat input can be provided to the hot gas stream (e.g., the turbine exhaust stream) by any of the combustion devices known in the art. Examples of suitable combustion devices include conduit burners, supplemental burners, or other conventional means for supplementing the heating of the flue gas.

In some aspects, the hot gas stream can be at a temperature higher than desired (i.e., the conversion process will be at a temperature above the desired temperature due to heat input from the hot gas stream). In such an aspect, the temperature of the hot gas stream can be lowered prior to contacting the reactor tube. A preferred method of reducing the temperature of the hot gas stream includes mixing the hot gas stream with a cooler gas stream (such as additional air and/or recycled cooling gas) and/or passing the hot gas stream through a heat exchanger. Excess heat from the hot gas stream may preferably be used to provide heat to the conversion process, preheating the fuel or the oxygen-containing gas stream, and/or generating a vapor.

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 catalyst fixed bed (which comprises a random and structured bed) within the tubes. Preferably, the reactor tube contains a fixed bed of catalyst composition and inert material. Fill and/or Suitable methods for designing a fixed bed of reactor tubes include US 8,178,075, which is incorporated by reference in its entirety. The reactor tube can include at least one internal structure (e.g., a concentric outer casing) to support the catalyst composition and/or reduce the pressure drop within the reactor tube. The reactor tube can include a mixing internal structure positioned within the reactor tube to provide mixing in the radial direction. The mixing internal structure can be positioned in the bed of the catalyst composition or in various portions of the reactor tube to separate the catalyst composition of two or more zones. 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 substantial isothermal temperature profile can be provided, which is measured along the centerline of the tube. Substantial advantage of the isothermal temperature distribution is to maximize the efficient use of the catalyst and make it useless C ₄ - a byproduct of the manufacturing advantage of minimizing. As used herein, "isothermal temperature distribution" means that the temperature at each point between the inlet of the reactor and the outlet of the reactor as measured along the centerline of the tube of the reactor remains substantially fixed, for example in 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 distribution 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 profile is wherein the reactor inlet temperature is within about 20% of 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 tube varies by no more than about 40 ° C, or no more than about 20 ° C, compared to the inlet temperature of the reactor. Or no more than about 10 ° C, or no more than about 5 ° C. Alternatively, the isothermal temperature profile is such that the temperature along the length of the reaction zone within the reactor is within about 20% of the reactor inlet temperature, or within about 10%, or within about 5%, or Within about 1% of the reactor inlet temperature.

However, to minimize catalyst passivation rate, it may be desirable to optimize the design of the conversion system to maintain a substantial inverse temperature distribution in the tubular reactor. As used herein, "inverse temperature distribution" 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 distribution" includes systems in which the temperature in the reactor 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. "Inverse temperature distribution" additionally encompasses a reactor tube having a centerline temperature T1: some length along the reactor tube Degreeally, the centerline temperature is lowered to a temperature T2; the centerline temperature is raised to a temperature T3 along a further length of the reactor tube; finally, the centerline temperature at the outlet of the reactor tube is lowered to a temperature T4; Where T3>T4>T1>T2.

The temperature measured at the point where the feedstock just contacts the catalyst composition near the inlet of the reactor is compared to the temperature measured at the point where the effluent does not contact the catalyst composition near the outlet of the reactor. It is between about 0 ° C and about 200 ° C low, preferably about 25 ° C to about 150 ° C, more preferably about 50 ° C to about 100 ° C. Preferably, the tube centerline temperature measured at the point where the material just contacts the catalyst composition near the inlet of the tube is at a point where the effluent does not contact the catalyst composition adjacent the outlet of the tube. The measured tube centerline temperature is between about 0 ° C and about 200 ° C lower, preferably between about 25 ° C and about 150 ° C, more preferably between about 50 ° C and about 100 ° C.

Maintaining a reverse temperature profile in the reactor tube advantageously minimizes the formation of carbonaceous material at the inlet which may contribute to coking of the catalyst composition. The reverse temperature profile can also provide sufficient reaction time and length in the reactor tube to provide sufficient reaction time and length at operating temperatures that are lower than the outlet temperature to minimize formation of carbonaceous material at the effluent outlet. H ₂ .

The conversion system may additionally include a heat transfer device for transferring additional heat from the hot gas stream (eg, the turbine exhaust) to other streams, such as a reactivation gas, a regeneration gas, the feedstock (before the feedstock enters the reactor tube) The fuel (eg, the fuel gas), the gas stream comprising oxygen, and/or vapor. The additional heat transfer device can be known in the art. Any suitable heat transfer device. Suitable heat transfer devices include heat exchange tube bundles. The heat transfer device can be positioned in the reactor tube seal such that before or after heat is transferred from the hot gas stream (eg, the turbine off-gas) to the reactor tube, additional heat is passed from the hot gas stream (eg, the turbine Exhaust gas) is delivered to the reactor tube.

The conversion system may additionally comprise two or more parallel reactor tube bundles within the convective heat transfer enclosure. The conversion system can include two or more enclosures, each of which contains a bundle of parallel reactor tubes containing a catalyst composition. The conversion system can also include means for controlling the flow of the hot gas stream (e.g., the turbine exhaust) to each of the clusters. Suitable flow control devices include control valves, baffles, louvers, dampers, and/or lines. The conversion system can also include the ability to divert at least a portion of the hot gas stream (eg, the turbine exhaust) to exit or surround the reactor tube and direct the hot gas stream (eg, the turbine exhaust) to other heat recovery devices or to exhaust gases chimney. The conversion system may also include auxiliary equipment such as exhaust muffler and scrubber.

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 amount of coke deposited on the catalyst during a conversion cycle is referred to as incrementally deposited coke. A reactivation cycle is used to remove at least a portion of the incrementally deposited coke material from the catalyst composition. The reactivation begins by stopping the flow of acyclic C5 feedstock to the reactor tube and reducing the transfer of heat from the hot gas stream (the turbine off-gas) by convection. The heat transferred from the hot gas stream (the turbine exhaust stream) to the reactor tube may be by limiting the flow of the hot gas stream (the turbine exhaust stream) and/or at least a portion of the hot gas stream (the turbine exhaust stream) Turning to lower away from the reactor tube. 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, an oxygen-containing inert compound such as CO does not react with the catalyst.

The flow of the reactivation gas may be in the same direction or in the opposite direction to the flow of the stopped material. 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 removes 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 suspension and resurrection gases starts to flow again and the non-cyclic C ₅ incremental starting material by convective heat transfer from the hot gas stream (e.g., the turbine exhaust gas) is.

The reactivation in the illustrated conversion system advantageously has ≦90 minutes, for example ≦60 minutes, ≦30 minutes, ≦10 minutes, such as ≦ 1 minute, or ≦ 10 seconds length of time. 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 to 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 rich in light hydrocarbons and a gas depleted of 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 to provide to the reactor tube. The separation apparatus can be a membrane system, an adsorption system (e.g., a pressure swing type and/or a temperature change type), or other systems 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 method, a number of carbonaceous material or coke forming material on the catalyst composition, it is not resurrected by a gas containing H ₂ of the resurrection anaerobically removed. Oxidative regeneration is used to remove at least a portion of this coke material from the catalyst composition. The regeneration cycle begins by stopping the flow of feedstock to the reactor tubes and reducing the heat transferred by the convection from the hot gas stream (the turbine off-gas). Use clean gas drive (e.g. N ₂₎ from the reactor tube chased combustible hydrocarbon gas, comprising a reactor feed or product (C ₅ acyclic and cyclic hydrocarbons). After the hydrocarbon flooding, 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 remove at least 10 wt% (≧ 10 wt%) of the coke material present at the beginning of regeneration by oxidation. The coke material is removed from about 10 wt% to about 100 wt%, preferably from about 90 wt% to 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. After chased oxygen, then flow may resume the non-cyclic C ₅ material, accompanied with the increased amount of heat transmitted by convection from the hot gas (the exhaust gas turbine).

Regeneration (including flooding before or after coke oxidation) requires less than about 10 days, preferably less than about 3 days to complete. The regeneration can be carried out from about once every 6 days to about once every 180 days, preferably from about once every 10 days to about once every 40 days.

Multi-body configuration

The conversion system may additionally comprise two or more parallel reactor tube bundles within the convective heat transfer enclosure. The conversion system can include two or more enclosures, each containing a parallel reactor tube bundle containing a catalyst composition. The conversion system can also include means for controlling the flow of the hot gas stream (e.g., the turbine exhaust) to each of the plexes. Suitable flow control devices include control valves, baffles, louvers, dampers, and/or conduits.

The conversion process described the conversion system may comprise a gas or regeneration gas resurrection provided to one or more parallel reactor tube bundle and while providing a feedstock comprising a non-cyclic C ₅ to hydrocarbons of one or more different reactors Tube bundles.

Figure 1 illustrates a possible configuration 220 for a plurality of reactors (reactor tube bundles) interconnected in parallel. 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 reactor (not all of each header of each reactor to the catheter is shown in Figure 1). The product can be collected from all of the reactors 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 reactors. Regeneration effluent header 205 can collect regeneration effluent from all of these reactors. Likewise, the resurrection effluent header 203 can collect the resurrection effluent from all of the reactors. Although the configuration of four (4) reactors is shown in Figure 1, the invention is not limited by this number. Multiple reactor configurations having 2, 3, 4, 5, 6, 7, 8, 9, 10, or more reactors are suitable for the present invention. A multi-reactor configuration with five (5) reactors is preferred.

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

Advantageously, the conversion method can comprise conversion in multiple reactors The system is used in the system for simultaneous “on-oil” material conversion, reactivation, and/or regeneration. 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 reactors, such as "on-oil" switching and reactivation of the reactors 210, 211, and 212, while at least one other reactor (e.g., reactor 213) is regenerated. . When regeneration of the reactor (e.g., reactor 213) is completed, it can be returned to the "on-oil" shift/reactivation cycle while another reactor (e.g., reactor 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 example aspect

The invention further relates to:

An example aspect of generating power and integrated method to convert the non-cyclic C ₅ C ₅ hydrocarbons to cyclic hydrocarbons, wherein the method comprises: a) compressing the gas stream containing oxygen; b) was compressed in the turbine the combustion gas stream to produce a fuel gas turbine and a power turbine exhaust stream; c) providing a feedstock comprising acyclic hydrocarbons of the C _5; D) such that the feedstock with a catalyst composition in a reaction tube in parallel, while by convection the heat from the turbine exhaust gas stream to the outer surface of the reactor wall; and e) obtain effluent comprising C ₅ cyclic hydrocarbon of the reactor, wherein the hydrocarbon comprises a cyclic C ₅ cyclopentadiene.

Example 2. The method of Example 1, wherein the reactor tube has an inverse temperature distribution.

The method of embodiment 1 or 2, wherein the feedstock and the turbine exhaust stream flow in the same direction to provide a heat flux near the inlet that is greater than a heat flux near the outlet of the reactor tube the amount.

The method of any of the examples 1 to 3, further comprising using the turbine power to i) rotate the generator to generate electricity and/or ii) rotate the compressor.

The method of any of the examples 1 to 4, further comprising combusting additional fuel gas with unreacted oxygen in the turbine exhaust stream to transfer heat by convection in step d) , increasing the temperature of the turbine exhaust stream.

The method of any one of clauses 1 to 5, wherein the contacting of the raw material with the catalyst is carried out in the presence of H ₂ , C ₁ , C ₂ , C ₃ , and/or C ₄ hydrocarbons. .

The method of any of the examples 1 to 6, further comprising facilitating heat transfer to the touch by providing fins or contours on the interior and/or exterior of the reactor tube Media composition.

Example 8. The method of Example 7, wherein the fin and/or the profile promotes a heat flux at the inlet that is greater than a heat flux at the outlet of the reactor tube.

The method of any of the examples 1 to 8, further comprising: mixing the raw material and the converted ring C in the radial direction by providing the internal device for mixing in the reactor tube ₅ hydrocarbon, wherein 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 catalyst composition.

The method of any one of clauses 1 to 9, wherein the contacting of the starting material with the catalyst composition occurs at a temperature of from about 450 °C to about 800 °C.

The method of any one of clauses 1 to 10, wherein the feed to the reactor tube has a temperature of from about 450 ° C to about 550 ° C at the reactor inlet.

The method of any one of clauses 1 to 11, wherein the reactor tube has an outlet pressure of from about 4 psia to about 50 psia during contact with the feedstock.

The method of any one of clauses 1 to 12, wherein the reactor tube is measured from the reactor inlet to the reactor outlet during contact with the feedstock, having a pressure drop of from about 1 psi to about 100 psi.

The method of any one of embodiments 1 to 13, wherein at least about 30% by weight of the acyclic C5 hydrocarbon is converted to cyclopentadiene.

The method of any one of aspects 1 to 14, wherein the catalyst composition comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum in citrate modified On the rock.

The method of Example 15, wherein the catalyst composition further comprises an inert material.

The method of any one of examples 1 to 16, wherein the catalyst composition is an extrudate having a diameter of from 2 mm to 20 mm.

Example of the method of any of the examples 1 to 17, wherein The cross-section of the catalyst composition is shaped to have one or more leaves and/or concavities.

Example 9. The method of Example 18, wherein the leaves and/or concaves of the catalyst composition are helical.

The method of any one of clauses 1 to 19, wherein the hourly weight space velocity is from 1 to 1000 hr ^{-1 in terms of the} amount of active catalyst in the reactor tube.

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

The method of any one of clauses 1 to 21, wherein i) the feedstock, regeneration gas, or reactivation gas system is directed to and from the reactor or the like via an inlet and outlet manifold.

The method of any one of clauses 1 to 22, further comprising: transferring additional heat from the turbine exhaust by convection to a reactivation gas, a regeneration gas, the feedstock, the fuel gas, the oxygen containing Airflow, and/or vapor.

The method of any of the examples 1 to 23, further comprising i) providing two or more parallel reactor tube bundles, the reactor tubes containing the catalyst composition and ii) resurrection gas or regeneration gas provided to the one or more reactor tubes plexus while feedstock comprising acyclic hydrocarbons of the C ₅ to provide one or more different tube bundle reactors.

The method of Example 25. Examples aspect according to any one of aspects 1 to 24, which further comprises: a) providing a feedstock comprising a non-stop cyclic C ₅ hydrocarbons and reduces the heat transmitted by convection from the exhaust gases of the turbine ; b) providing a reactivation gas comprising H ₂ ; c) contacting the reactivation gas with the catalyst composition to remove at least a portion of the coke material on the catalyst composition; and d) stopping providing the reactivation gas and providing a feed resumed acyclic C ₅ hydrocarbons and increases the heat transmitted by convection from the exhaust gases of the turbine.

Example Aspect 26. The method of Example Aspect 25, wherein the duration of steps a) through d) is 1.5 hours or less.

The method of claim 25 or 26, wherein contacting the reactivation gas system occurs at a temperature of from about 500 ° C to about 900 ° C.

The method of any one of clauses 25 to 27, wherein the reactor tube has an outlet pressure of from about 5 psia to about 250 psia when contacted with the reactivation gas.

The method of claim 25 or 26, wherein contacting the reactivation gas system occurs at a temperature of from about 575 ° C to about 750 ° C.

The method of any one of clauses 25, 26, or 29, wherein the reactor tube has an outlet pressure of from about 25 psia to about 250 psia when contacted with the reactivation gas.

The method of any one of clauses 25 to 30, wherein the coke is incrementally deposited and at least 10% by weight of the incrementally deposited coke material is removed from the catalyst composition.

The method of Example 32. Examples aspect in any one of aspects 1-31, which further comprises: a) providing a feedstock comprising a non-stop cyclic C ₅ hydrocarbons and reduces the heat transmitted by convection from the exhaust gases of the turbine b) purging any combustible gas from the reactor tubes, including the feedstock and reactor products; c) contacting the regeneration gas comprising the oxidation material with the catalyst composition to remove at least a portion by oxidation a coke material on the catalyst composition; d) driving the regeneration gas from the reactor tubes; and e) stopping the regeneration of the regeneration gas and restarting the supply of the raw material containing the acyclic C ₅ hydrocarbons The heat transferred from the turbine exhaust by convection.

Examples of aspect 33. A power generating and converting the non-cyclic C ₅ C ₅ hydrocarbons to cyclic hydrocarbons integrated switching system, wherein the system comprises: a) a compressor for compressing the gas stream containing oxygen; b) turbine for the turbine to the compressed gas stream combusting fuel gas to produce turbine power and a turbine exhaust stream; c) a feedstream comprising a non-cyclic C ₅ to hydrocarbon; D) comprising parallel catalyst composition of the reactor tube; and e) produced by following the C ₅ hydrocarbon comprises a cyclic reactor effluent stream: at least a portion of said feedstock is contacted with the catalyst composition (s) parallel to the reactor tube, by both the turbine exhaust stream to transfer heat (preferably by convection) to the outside wall surface of the reactor, wherein the hydrocarbon comprises a cyclic C ₅ cyclopentadiene.

Example. The system of example aspect 33, wherein the reactor tube has an inverse temperature distribution.

The system of example aspect 33 or 34, wherein the feedstock and the turbine exhaust stream flow in the same direction to provide a heat flux at the inlet that is greater than a heat flux at the outlet of the reactor tubes .

The system of any of the examples 33 to 35, further comprising at least one combustion device that inputs additional thermal energy into the turbine exhaust stream.

</ RTI> The system of any one of examples 33 to 36, further comprising fins or profiles on the interior or exterior of the reactor tubes to facilitate heat transfer to the catalyst composition.

The system of any one of examples 33 to 37, further comprising a mixing internal device positioned within the reactor tube to provide mixing in a radial direction, wherein the mixing internal device is positioned i) in the catalyst composition bed or ii) in the various portions of the reactor tubes to separate the catalyst composition of two or more zones.

The system of any one of examples 33 to 38, wherein the catalyst composition comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum in citrate modified On the rock.

Example. The system of example aspect 39, wherein the catalyst composition further comprises an inert material.

The system of any one of examples 33 to 40, wherein the catalyst composition is an extruded body having a diameter of 2 mm to 20 mm.

The system of any one of examples 33 to 41, wherein the cross-section of the catalyst composition is shaped to have one or more leaves and/or concavities.

Example Aspect 43. The system of example aspect 42, wherein the leaves and/or concavities of the catalyst composition are helical.

The system of any one of examples 33 to 43 wherein the diameter of the reactor tubes is from about 20 mm to about 200 mm.

The system of any one of examples 33 to 44, further comprising an inlet and outlet manifold in fluid communication with the reactor tubes, wherein the feedstock, regeneration gas, or reactivation gas system is passed through the inlet And the outlet manifold is directed to and from the reactor tubes.

The system of any one of examples 33 to 45, further comprising: for transferring additional heat from the turbine exhaust by convection to the reactivation gas, the regeneration gas, the feedstock, the fuel gas, the A heat transfer device comprising a stream of oxygen, and/or a vapor.

The system of any one of examples 33 to 46, further comprising a generator and/or a compressor for generating electrical power, wherein the generator and/or compressor is powered by the turbine.

The system of any one of examples 33 to 47, further comprising i) two or more parallel reactor tube bundles, the reactor tubes containing the catalyst composition and ii) provided to one or more reactor tubes of the bundle or regeneration gas stream resurrection, wherein the feedstock comprises a C ₅ acyclic hydrocarbons are simultaneously supplied to the plurality of reactors or a different tube bundle.

The system of any one of examples 33 to 48, further comprising: a) a reactivation gas stream comprising H ₂ ; and b) for contacting the reactivation gas with the catalyst composition to remove A device for coke material on at least a portion of the catalyst composition.

The system of any one of examples 33 to 49, further comprising: a) a purge stream comprising an inert gas and a regeneration gas stream comprising an oxidation material; and b) a device for use And i) removing any combustible gas from the reactor tubes, including the feedstock and reactor products, and ii) contacting the regeneration gas with the catalyst composition to remove at least a portion of the catalyst by oxidation Coke material on the composition.

Industrial applicability

Any combination of cyclic, branched, and linear C ₅ hydrocarbons contained during the acyclic C ₅ conversion process and optionally containing hydrogen, C ₄ and light by-products, or 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 more (or preferably 60 wt% or more) of 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 product, which is based on the following reaction scheme Figure (I) is formed: 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 monoolefin described in the scheme (I), a purified product containing 80% by weight or more (or preferably 90% by weight or more) of CPD can also be used. Logistics to form DDT-Adel reaction products of CPD and one or more of the following: other CPD molecules, conjugated dienes, alkynes, heavy olefins, disubstituted olefins, trisubstituted olefins Classes, cyclic olefins, and substituted forms of the foregoing. Preferred Dier-Adel reaction products include norbornene, ethylidene norborene, substituted norbornenes (including oxygen-containing primary olefins), norbornadienes And tetracyclododecene, as depicted in the following structures:

The aforementioned Diles-Alder reaction product is a copolymer of a cyclic olefin used for the production of a polymer and copolymerization with an olefin such as ethylene. The obtained cyclic olefin copolymer and cyclic olefin polymer product are useful For a variety of applications such as packaging films.

Purified product streams containing 99 wt% or higher of 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 converted to the product line for high carbon olefins and alcohols. Cyclic and non-cyclic C ₅ product, optionally after hydrogenation, as components based composition for delivering fuel and blending octane enhancer.

[Example]

The following examples depict the invention. A variety of modifications and variations are possible, and it is to be understood that the invention may be practiced otherwise than as specifically described herein within the scope of the appended claims.

Example 1

Reference to FIG. 2, comprises a non-cyclic C ₅ hydrocarbon feedstock 10 is supplied to the seal 20 in the parallel reactor tube 23 thereof. This material is contacted inside 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 product or for further processing.

The gas stream 60 containing oxygen is compressed in the compressor 61. Fuel gas 62 is combined with the compressed gas in the compressor 61 and combusted in turbine 63 to produce turbine power 64 and turbine exhaust stream 70. Optionally, additional fuel gas 82 is supplied to the additional combustion unit 81 in the enclosure 80, wherein the additional fuel gas 82 is combusted with unreacted oxygen in the turbine exhaust stream to increase the temperature of the turbine exhaust stream. . Turbine power 64 is used to rotate compressor 61 and rotate a generator (not shown) to generate electricity.

At least a portion of the turbine exhaust stream 70 is directed via conduit 71 to the enclosure 20, wherein heat is transferred by the turbine exhaust stream 70 to the outer surface of the walls of the reactor tubes 23 by convection. The feedstock 10 and turbine exhaust stream 70 flow in the same direction within the enclosure 20 to provide a higher heat flux near the inlet of the reactor tube 23 and a lower heat flux near the outlet of the reactor tube 23. . The reactor tube 23 has an inverse temperature distribution. The temperature and flow rate of the turbine exhaust stream 70 directed to the enclosure 20 is controlled based on the temperature of the desired reactor effluent 32 exiting the reactor tube 23.

The additional heat is transferred by convection from the turbine exhaust stream 70 within the enclosure 20 to heat i) the feedstock 10 in the exchanger 12, ii) the reactivation gas 41 in the exchanger 42, and iii) In the switch 91 The vapor in the 90. An additional exchanger (not shown) arbitrarily transfers turbine waste heat to fuel gas 62, regeneration gas 53, and/or oxygen-containing gas stream 60. The heated vapor produced in exchanger 91 is directed away via conduit 92 for additional use as a utility stream. The cooled exhaust stream 72 is conducted away from the enclosure 20 via conduit 26.

Feedstock 10 is directed to exchanger 12 via conduit 11 and is preheated to about 450 ° C to about 550 ° C and is directed to reactor tube 23 by exchanger 12 via conduit 13, inlet manifold 14, and conduit 15. Feedstock 10 is contacted with a catalyst composition (not shown) in reactor 23 at a temperature of from about 450 °C to about 800 °C. The outlet pressure of the (equal) reactor tube 23 is maintained between about 4 psia to about 50 psia during the contact. 10 and the raw material converted cyclic C ₅ hydrocarbons (e.g., cyclopentadiene) by mixing internals of the reactor tube 23 in such internal device (not shown) are mixed in the radial direction. At least about 30% by weight of the acyclic C5 hydrocarbon in feedstock 10 is converted to cyclopentadiene. The pressure drop across the reactor tube 23 as measured by the reactor inlet 16 to the reactor outlet 33 during contacting is from about 1 psi to about 100 psi.

The flow of feedstock 10 can be stopped and the flow of turbine exhaust 70 can be reduced or turned for reactivation. 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 exchanger 42 and directed via conduit 43, inlet manifold 14, and conduit 15 to reactor tube 23. The reactivation gas 45 is contacted within the reactor tube 23 at about 400 ° C to about 800 ° C with the catalyst composition (not shown) to remove at least a portion of the coke material from the catalyst composition. The outlet pressure of reactor tube 23 during contact with reactivation gas 45 is from about 5 psia to about 250 psia. 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 conducted to the reactivation system 40 via conduit 30, outlet manifold 31, and conduit 44. Within the reactivation system 40, the regenerated 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. Gas and light hydrocarbons are produced by depleted gas. The light hydrocarbon gas (not shown) is carried away for use as a fuel gas in particular. The light hydrocarbon depleted stream (also not shown) is combined with fresh reactivation gas 45 in reactivation system 40 and supplied to reactor tube 23. After the coke is sufficiently removed, the flow of the reactivation gas 45 is stopped and the supply of the raw material 10 is resumed and the flow of the turbine exhaust gas 70 is increased.

The flow of the feedstock 10 can be stopped and the flow of the turbine exhaust gas 70 can be reduced for regeneration. The purge gas 54 is supplied via the regeneration system 50 and the conduit 51. 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 (for example, air) containing the material for oxidation is supplied via the regeneration system 50 and the conduit 51. The regeneration gas 53 is directed to the reactor tube 23 via the conduit 51, the inlet manifold 14, and the 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 of the regeneration gas 53. . The regeneration effluent exits the reactor tube 23 and is conducted to the regeneration system 50 via conduit 30, outlet manifold 31, and conduit 52. When enough of the coke has been removed (e.g., has been removed at least 10wt% of coke) or when no further oxidation of these by oxidation product leaving the reactor tube 23 of a low concentration (such as CO or CO ₂₎ during the detection, The flow of the regeneration gas 53 is stopped. The flow of the purge gas 54 is restarted to drive the regeneration gas from the reactor tubes 23. After the purge, the flow of the feedstock 10 and the flow of the turbine exhaust gas 70 are resumed.

Reference to FIG. 3, an integrated switching system and method for generating power and convert non-cyclic C ₅ hydrocarbon cyclic C ₅ hydrocarbons become. The conversion system 101 includes a filter 100 that filters a gas stream containing oxygen (air) that is directed to a compressor 105. The compressed air is combusted in turbine 110 with fuel gas (not shown). Expanding the combustion gases inside the turbine 110 produces turbine power and turbine exhaust streams (not shown). The turbine power rotates the compressor 105 and the generator 160 that produces electricity. A combustion device 120 including a duct burner 121 provides additional heat input to the turbine exhaust stream. Heat from the turbine exhaust stream is passed to reactor tube 131 by convection. Based feed stream comprising a non-cyclic C ₅ hydrocarbons (not shown) of the guide tube 131 to the reactor via the inlet manifold 130. The feedstock is contacted with a catalyst composition (not shown) in reactor tube 131 and reactor effluent (also not shown) exits reactor tube 131 via outlet manifold 132. Before the turbine exhaust exits the chimney 152 containing the exhaust muffler 153, the heat transfer device 140 containing the heat transfer exchanger tubes allows additional heat to be transferred by the turbine exhaust by convection.

The reactivation gas and/or regeneration gas 141 is heated in the heat transfer device 140 and directed to the reactor tube 131 via the conduit 142. Convection The heat transferred to the reactor tube 131 can be reduced by closing the baffle 116 and opening the baffle 115, which again directs at least a portion of the turbine exhaust gases away from the reactor tube 131 and past the muffler containing 151 Pass the chimney 150.

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 mixed 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 synthesized material (not shown) shows the typical pure phase of ZSM-5 phase theory. SEM (not shown) of the synthesized material showed that the material consisted of a crystal mixture having a thickness of 0.5-1 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. The atmosphere subsequently changed gradually 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, 0.29 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 profiles: a substantially isothermal temperature profile and an inverse temperature profile. The catalyst (0.5 g) was physically mixed with quartz (1.5 g, 60-80 mesh) and filled in a 3/8" OD, 18" long stainless steel reactor. The catalyst bed is held in place with the quartz wood 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 used to maintain the isothermal temperature profile 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 for maintaining the reverse temperature distribution 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 to test for the gradient and linear temperature gradient was 500 deg.] C to 600 deg.] C of. The performance results for Example 3 are shown in Figures 4 and 5.

As shown in Figure 4, the operation of the reactor in an inverse or gradient temperature distribution (i.e., at a lower temperature of the inlet and a higher temperature at the outlet) allows the catalyst to operate isothermally at the same outlet temperature. The reactor has a higher stability. In particular, FIG. 4 shows: Although cyclic C ₅ total yield of the first two kinds of temperature distributions are similar, and the like having a temperature profile of the temperature of the reactor, the yield is reduced to 53 hours after the initial value of 43% of its original . In contrast, the yield in the inverse temperature distribution 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 5, when it is desired that the minimum byproduct C ₁ -C ₄ hydrocarbon cracking product yield, etc. The ratio of the operating temperature of the reactor using an inverse temperature profile or gradient 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. SEM (not shown) of the composite material shows that the material consists of a mixture of large crystals having a size < 1 micron. The resulting ZSM-5 crystal has a SiO ₂ /Al ₂ O ₃ molar ratio of >800 and ~0.28% Na, and 0.9 wt% Ag.

This material was calcined in nitrogen at 482 ° C 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. Cooling Thereafter, 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 350 ° C for 3 hours in air. The catalyst powder was compressed (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, 50 psia of C ₅ H ₁₂ , 1:1 molar H ₂ : C ₅ , 14.7 WHSV, total 45 psia during the oil. The test conditions for the intermittent H ₂ revival strategy were the following: the reactor was on oil for 1 hour and revived on H _{2 for} 1 hour (200 cm ³ min ^-1 H ₂ at 600 ° C and full H ₂ at 45 psia) Under the conditions, that is, without another He) cycle. The performance results for the two operating strategies are shown in Figure 6 as the address-time-yield of the cyclic C5 (i.e., cC5 moles/Pt moles per second). Figure 6 depicts the ability H ₂ resurrection catalyst can improve the C ₅ hydrocarbons by catalytic cyclization.

All documents described herein are incorporated herein by reference to the extent that they do not contradict this text, including any priority documents and/or test procedures. The invention has been described and described in detail by the foregoing general description and the specific embodiments of the invention. Therefore, it is not intended that the invention be limited thereby. Similarly, the term "comprising" is synonymous with the term "including". Similarly, whenever there is a transitional phrase "contains" in front of a group of components, elements, or elements, it is understood that we also consider that the composition or group of elements has a transitional phrase "consisting essentially of", "Consisting of", "selected from a group consisting of" or "Yes" precedes the listing of the constituent elements or elements, and vice versa.

Claims (28)

A non-cyclic C ₅ hydrocarbons method of converting cyclic hydrocarbon of C _5, wherein the method comprises: a) compressing the gas stream containing oxygen; b) the compressed gas stream to oxidize the fuel to produce hot gas stream; c) providing a the non-cyclic C ₅ hydrocarbon feedstock (feedstock); d) the feedstock and the catalyst composition is contacted in reactor tubes in parallel, while the heat by convection from the hot gas stream to the outer wall of the reactor surface; and e) obtain effluent comprising C ₅ cyclic hydrocarbon of the reactor, wherein the hydrocarbon comprises a cyclic C ₅ cyclopentadiene. A method of generating power and integrated method of converting a non-cyclic C ₅ C ₅ hydrocarbons to cyclic hydrocarbons, wherein the method comprises: a) compressing the gas stream containing oxygen; b) in the turbine to the combustion of the fuel gas stream compressed gas to generate turbine power and a hot gas stream, wherein the hot gas is a turbine exhaust stream; c) providing a raw material comprising a non-cyclic C ₅ to hydrocarbon; D) such that the feedstock with a catalyst composition in a reaction tube parallel, while by convection heat from the turbine exhaust gas stream to the outer surface of the reactor wall; and e) the reactor effluent is obtained comprising a cyclic hydrocarbon of C _5, C ₅ wherein the cyclic hydrocarbon comprises cyclopentadiene . The method of claim 1 or 2, wherein the reactor tube has an inverse temperature profile or an isothermal temperature profile. The method of claim 1 or 2, wherein the feedstock and the hot gas stream flow in the same direction to provide a heat flux near the inlet that is greater than a heat flux near the outlet of the reactor tube. The method of claim 1 or 2, further comprising: combusting the additional fuel with unreacted oxygen in the hot gas stream to increase the hot gas stream prior to transferring heat by convection in step d) temperature. The method of claim 1 or 2, wherein the contacting of the raw material with the catalyst composition is carried out in the presence of H ₂ , C ₁ , C ₂ , C ₃ , and/or C ₄ hydrocarbons. The method of claim 1 or 2, further comprising providing fins or contours on the interior and/or exterior of the reactor tube to facilitate heat transfer to the catalyst composition . The method of claim 7, wherein the fin and/or the profile promotes a heat flux near the inlet that is greater than a heat flux at the outlet of the reactor tube. The method of claim 1 or 2, further comprising mixing the raw material and the converted cyclic C ₅ hydrocarbon in a radial direction by supplying a mixing internal to 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 catalyst composition. The method of claim 1 or 2, wherein contacting the raw material with the catalyst composition occurs at a temperature of from 450 ° C to 800 ° C. For example, the method of claim 1 or 2, wherein the reaction The tube has an outlet pressure of 4 psia to 50 psia during contact of the feedstock with the catalyst composition. The method of claim 1 or 2 wherein the reactor tube has a pressure drop from 1 psi to 100 psi measured from the reactor inlet to the reactor outlet during contacting of the feedstock with the catalyst composition. The method of claim 1 or 2, 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 or 2, wherein the catalyst composition is an extruded body having a diameter of from 2 mm to 20 mm. The method of claim 1 or 2, wherein the cross-section of the catalyst composition is shaped to have one or more leaves and/or concavities, and wherein the catalyst composition has a leaf and/or concave spiral Spiraled or straight. The method of claim 1 or 2, wherein the inner diameter of the reactor tube is from 20 mm to 200 mm. The method of claim 1 or 2, further comprising transferring additional heat from the hot gas stream by convection to a rejuvenation gas, a regeneration gas, the feedstock, the fuel, the oxygen-containing gas stream, and / or steam. The method of claim 1 or 2, further comprising i) providing two or more parallel reactor tube bundles, the reactor tubes containing a catalyst composition and ii) providing a reactivation gas or a regeneration gas to one or more reactor tubes plexus and the non-cyclic C ₅ comprising a feedstock of hydrocarbons to provide one or more different tube bundle reactors. The method of claim 1 or 2, further comprising: a) discontinuing the supply of the raw material comprising the acyclic C ₅ hydrocarbon and reducing the heat transferred from the hot gas stream by convection; b) providing H comprising _a reactivation gas; c) contacting the reactivation gas with the catalyst composition to remove at least a portion of the coke material on the catalyst composition; and d) stopping providing the reactivation gas and restarting providing the acyclic The C ₅ hydrocarbon feedstock and the heat transferred from the hot gas stream by convection. The method of claim 1 or 2, further comprising: a) stopping providing a raw material comprising acyclic C ₅ hydrocarbons and reducing heat transferred from the hot gas stream by convection; b) by such The reactor tube purges any combustible gas comprising the feedstock and the reactor product; c) contacting the regeneration gas comprising the oxidation material with the catalyst composition to remove at least a portion of the catalyst composition by oxidation a coke material; d) driving the regeneration gas from the reactor tubes; and e) stopping the regeneration of the regeneration gas and restarting the supply of the raw material containing the acyclic C ₅ hydrocarbons and increasing the heat from the convection The heat transferred by the stream. A method of generating power and converting the non-cyclic C ₅ hydrocarbons to C ₅ cyclic hydrocarbon conversion integrated system, wherein the system comprises: a) a compressor for compressing the gas stream containing oxygen; b) a turbine for in the turbine to the compressed gas stream combusting fuel gas to produce turbine power and a turbine exhaust stream; c) a feedstream comprising a non-cyclic C ₅ to hydrocarbon; D) comprising of parallel catalyst composition of the reactor tube; and e) manufactured by following the C ₅ hydrocarbon comprises a cyclic reactor effluent stream: pipe manipulation of at least a portion of the feedstock is contacted with the catalyst composition (s) parallel reactors, while from the exhaust gas stream of the turbine heat transfer (preferably by convection) to the outside wall surface of the reactor, wherein the hydrocarbon comprises a cyclic C ₅ cyclopentadiene. The method of claim 1 or 2, wherein the catalyst composition is formed into a structured catalyst shape. The raw material is supplied to at least one adiabatic reaction zone, as in the method of claim 1 or 2, which further comprises the contacting in d). The method of claim 22, further comprising providing the feedstock to the at least one adiabatic reaction zone prior to the contacting in d). The method of claim 1, wherein the oxidation of b) is performed in a turbine, a fuel cell, a furnace, a boiler, an excess air burner, and/or a fluidized bed, and wherein The fuel is selected from the group consisting of coal, fuel oil, hydrogen, methane, and mixtures thereof. An article derived from a product produced by the method of any one of claims 1 to 20 or 22 to 25, wherein the article is composed of a product and a reaction containing a double bond (substrate Derived from materials derived from the Diels-Alder reaction. The article of claim 26, wherein the product is selected from the group consisting of cyclopentadiene, dicyclopentadiene, cyclopentene, cyclopentane, pentene, Pentadiene, norbornene, tetracyclodocene, substituted decenes, Dier-Adel reaction derivatives of cyclopentadiene, cyclic olefin copolymers, cyclic olefin polymers , polycyclopentene, unsaturated polyester resin, hydrocarbon resin adhesive, blended epoxy resin, polydicyclopentadiene, and norbornene or substituted norbornene or dicyclopentane A metathesis polymer of olefin or any combination thereof. An article of claim 26, wherein the object is a wind turbine blade.