Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process

Abstract

Disclosed is a method for producing olefins and aromatic compounds from a hydrogen lean carbon containing feed, the method comprising hydropyrolyzing the hydrogen lean carbon containing feed in the presence of a hydrogen donor feed under reaction conditions sufficient to produce a product comprising olefins and aromatic compounds or a hydrocarbonaceous stream, wherein the hydrocarbonaceous stream is further processed into olefins and aromatic compounds, wherein the olefins and aromatic compounds from (i) or the hydrocarbonaceous stream from (ii) are each obtained by hydrogenation of the hydrogen lean carbon containing feed with the hydrogen donor feed and cracking of carbonaceous compounds comprised in the hydrogenated feed, and wherein the hydrogen donor feed comprises a compound that donates hydrogen to carbonaceous compounds in the hydrogen lean feed.

Claims

1. A method for producing olefins and aromatic compounds from a hydrogen lean carbon containing feed, the method comprising: hydropyrolyzing the hydrogen lean carbon containing feed comprising carbonaceous compounds in the presence of a catalyst comprising a mixture of a spent FCC catalyst and a ZSM-5 catalyst and a hydrogen donor feed at a temperature of 400 C. to 700 C. in a first stage of a reactor to produce a product comprising: (i) olefins and aromatic compounds; or (ii) a hydrocarbonaceous stream, wherein the hydrocarbonaceous stream is further processed into olefins and aromatic compounds, wherein the olefins and aromatic compounds from (i) or the hydrocarbonaceous stream from (ii) are each obtained by hydrogenation of the hydrogen lean carbon containing feed with the hydrogen donor feed to produce a hydrogenated feed and cracking of carbonaceous compounds comprised in the hydrogenated feed, the cracking of carbonaceous compounds comprised in the hydrogenated feed results in un-cracked or cracked hydrogenated feed, wherein the hydrogen donor feed comprises at least one compound that donates hydrogen to the carbonaceous compounds in the hydrogen lean carbon containing feed, said at least one compound being a compound other than H.sub.2, wherein the hydrogen lean carbon containing feed is selected from the group consisting of plant material and aquatic material, or a mixture thereof and the compound in the hydrogen donor feed that donates hydrogen to the carbonaceous compounds in the hydrogen lean carbon containing feed is a polymer, wherein the hydropyrolyzing is conducted at a pressure of about 17.5 MPa, and wherein a catalyst to feed ratio, defined as a mass ratio between the catalyst and a mixture of the hydrogen lean carbon containing feed and the hydrogen donor feed, ranges from 6.01 to 9.02 g/g.

2. The method of claim 1, wherein the method further comprises reforming carbon compounds from the un-cracked or cracked hydrogenated feed to aromatic compounds.

3. The method of claim 1, wherein the hydrogen lean carbon containing feed consists of aquatic material.

4. The method of claim 1, wherein the polymer is selected from the group consisting of a polyolefin, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyamide, polycarbonate, polyurethane, and polyester, or any combination thereof.

5. The method of claim 1, wherein the spent FCC catalyst is selected from the group consisting of X zeolites, Y zeolites or USY zeolites, mordenite zeolites, faujasite zeolites, nano-crystalline zeolites, MCM framework mesoporous materials, SBA-15 mesoporous silica, silico-alumino phosphate, gallophosphate, titanophosphate, or any combination thereof as is, or present in an active or inactive state.

6. The method of claim 5, wherein a combination of the hydrogen lean carbon containing feed and the hydrogen donor feed comprises greater than 12 wt. % of hydrogen.

7. The method of claim 1, wherein the reactor further comprises a second stage, and wherein one or more of the following reactions occur(s) in the first stage of the reactor or in the second stage of the reactor: (a) removal of side chains present in mono-aromatic compounds present in the un-cracked or cracked hydrogenated feed; (b) aromatization of paraffins, olefins, or naphthenes present in the un-cracked or cracked hydrogenated feed; (c) hydrogenation of coke or minimization of coke formation; (d) isomerization of compounds present in the un-cracked or cracked hydrogenated feed; or (e) hydrodeoxygenation of compounds present in the un-cracked or cracked hydrogenated feed to aromatic compounds.

8. The method of claim 1, wherein a weight ratio of the spent fluid catalytic cracking (FCC) catalyst to the ZSM-5 catalyst is 3:1.

9. The method of claim 1, wherein the aquatic material has a hydrogen content of 3, 2, 1, or less than 1 wt. %.

10. The method of claim 2, wherein the aquatic material has a hydrogen content of 3, 2, 1, or less than 1 wt. %.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Features and advantages of the methods and apparatus of the present invention will be more fully appreciated by reference to the following detailed description of presently preferred but nonetheless illustrative embodiments of the present invention when taken in conjunction with the accompanying drawings.

(2) FIG. 1 depicts a schematic representation of an embodiment of processing a hydrogen lean carbon containing feed in a single stage process.

(3) FIG. 2 is a schematic of an embodiment of a system that includes a multiple stage reactor.

(4) FIG. 3 illustrates some of the chemicals that can be produced from (A) ethylene, (B) propylene, (C) benzene, (D) toluene, and (E) xylenes.

(5) FIG. 4 depicts a schematic representation of an embodiment of processing multiple hydrogen lean carbon containing feeds.

(6) FIG. 5 depicts a schematic representation of an embodiment of using ammonia or urea as a hydrogen donor feed.

(7) FIG. 6 is a graphical representation of the wt. % of methane and ethylene versus wt. % sand in the catalyst.

(8) FIG. 7 is a graphical representation of the wt. % of C.sub.2, C.sub.3, and C.sub.4 olefins versus wt. % sand in the catalyst.

(9) FIG. 8 is a graphical representation of wt. % of heavies (hydrocarbons having a boiling point of 370 C. or more), versus wt. % sand in the catalyst.

(10) FIG. 9 is a graphical representation of wt. % of total olefins versus wt. % sand in the catalyst mixture.

(11) FIG. 10 is a graphical representation of wt. % of coke versus wt. % sand in the catalyst mixture.

(12) FIG. 11 is a graphical representation of wt. % of olefins in a gaseous stream containing hydrogen gas and C.sub.4 or less hydrocarbons versus wt. % sand in the catalyst mixture.

(13) FIG. 12 is a graphical representation of wt. % of aromatics boiling below 240 C. versus wt. % sand in the catalyst mixture.

(14) FIG. 13 is a graphical representation of wt. % of paraffins boiling below 240 C. versus wt. % sand in the catalyst mixture.

(15) FIG. 14 is a graphical representation of wt. % of iso-paraffins boiling below 240 C. versus wt. % sand in the catalyst mixture.

(16) FIG. 15 is a graphical representation of wt. % of napthenes boiling below 240 C. versus wt. % sand in the catalyst mixture.

(17) FIG. 16 is a graphical representation of wt. % of liquid olefins boiling below 240 C. versus wt. % sand in the catalyst mixture.

(18) FIG. 17 is a graphical representation of reaction bed temperature in degree Centigrade versus elapsed time after feed charged in seconds.

(19) While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. The drawings may not be to scale. It should be understood that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed, but to the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the present invention as defined by the appended claims.

DETAILED DESCRIPTION

(20) While hydropyrolysis of biomass and other unconventional carbon sources is known, the yield and quality of producing olefins and aromatics from such feedstocks remains largely inefficient. One potential cause of this is the instability of the intermediates produced during the hydropyrolyzing process. For example, during pyrolysis of biomass, formation of radicals may cause polymerization of molecules or coking or both. Conventional processes add molecular hydrogen during the pyrolysis process to control the polymerization and coking reactions. H.sub.2 is also used as a hydrogen source for hydrogenation of the products resulting from the pyrolysis reactions. The use of molecular hydrogen (hydrogen gas or H.sub.2) may be economically undesirable due to the cost of producing and storing hydrogen gas.

(21) The present discovery offers a solution to these inefficiencies by using hydrogen rich carbonaceous streams as a hydrogen donor source during the hydropyrolysis of hydrogen lean carbonaceous streams. The hydropyrolysis may be a single-stage or a multi-stage process. By single-stage, it is meant that olefins or aromatics, or both, can be produced directly from the hydropyrolysis step. By multi-stage, it is meant that the product produced from hydropyrolysis (e.g., intermediate hydropyrolyzed product) can be further processed in a second stage or second reaction to produce the desired olefins or aromatics, or both.

(22) These and other non-limiting aspects of the present invention are provided in the following subsections.

(23) A. Hydrogen Lean and Hydrogen Donor Feeds

(24) Hydrogen lean carbon containing feeds in the context of the present invention can include, but are not limited to, biomass, tires, sewage sludge, municipal solid waste, paper, coal, oil sands, oil shale, heavy petroleum oils, bio oils, pyrolysis oils produced as a result of pyrolysis of biomass, plastics, algal oils plant seed oils, oils and residues form plant or animal source, or any combination of the above. Biomass includes, but is not limited to, plant material, tree material, aquatic material, or any combination thereof. In a preferred embodiment, the hydrogen lean carbon containing feed is biomass. The hydrogen lean carbon containing feed of the present invention has an atomic hydrogen (H) content of 12 wt. % or less, about 10 wt. % or about 5 wt. %. In a preferred embodiment, the hydrogen lean carbon containing feed has a hydrogen content from about 7 wt. % to about 9 wt. %.

(25) A hydrogen donor feed stream in the context of the present invention includes compounds that are capable of donating an atomic hydrogen to the carbonaceous compounds in the hydrogen lean carbon containing feed. While hydrogen gas can be supplemented or added to the hydrogen donor feed, hydrogen gas is not needed in said hydrogen donor feed stream. Rather, compounds capable of donating atomic hydrogens can be used in the context of the present invention as the hydrogen donor source. Such compounds can be hydrocarbons, oligomers, polymers, ammonia, urea, or any combination thereof. Not to be bound by theory, it is believed that the compounds in the hydrogen donor feed react with one another to provide atomic hydrogen (for example, hydrogen radicals) to the carbonaceous compounds in the hydrogen lean carbon containing feed. Examples of hydrocarbons include, but are not limited to, natural or synthetic hydrocarbons, hydrocarbon gas having a carbon number from 1 to 4 (C.sub.1 to C.sub.4), naphtha or diesel liquids, synthetic hydrocarbons (for example, Fischer-Tropsch liquids), wax, grease, hydrogen donor solvents, or any combination thereof. Polymers include virgin or waste polymers. In a preferred embodiment, the hydrogen donor feed is substantially polymeric compounds or a mixture of polymers. Examples of polymers include thermosetting polymers, thermoplastic polymers, elastomers, synthetic fibers, polyethylene, poly(ethylene oxide) polymers, polypropylene, polyvinyl chloride, polystyrene, polyurethanes polyamides, polyacrylnitriles, poly(ethylene terephthalate), copolymers, plastics, and the like. The hydrogen donor feed stream has a total atomic hydrogen (H) content of greater than 12 wt. % (e.g., 12.1, 12.5, 13, 14, 15, 16, 17, 18, 19, 20 wt. % or more). In a preferred embodiment, the hydrogen donor feed has a hydrogen content from greater than 12 wt. % to 20 wt. %, or 13 wt. % to 17 wt. %. In still more particular aspects, the hydrogen donor feed can include about 1 wt. % or less of molecular hydrogen, about 0.5 wt. % or less of molecular hydrogen, or about 0.001 wt. % or less of molecular hydrogen.

(26) A hydrogen rich carbon containing feed, which can be the same as a hydrogen donor feed stream, can include plastics, polymers, hydrocarbons, etc., having a total atomic hydrogen content of greater than 12 wt. % (e.g., 12.1, 12.5, 13, 14, 15, 16, 17, 18, 19, 20 wt. % or more). In a preferred embodiment, the hydrogen rich carbon containing feed stream has a hydrogen content from greater than 12 wt. % to 20 wt. %, or 13 wt. % to 17 wt. %. The hydrogen rich carbon containing feed can be used in the context of the present invention without a hydrogen donor feed stream. Instead, the hydrogen rich carbon containing feed can be pyrolyzed to directly produce the desired aromatic or olefin compounds, or a combination of such compounds. In instances when a catalyst is used, hydrogen (H.sub.2) can be used with a hydrogen rich carbon containing feed or hydrogen donor feeds to alter agglomeration of material on the catalyst or activate the catalyst.

(27) B. Single Stage and Multi-Stage Processes

(28) Single stage and multi-stage processes can be used in the context of the present invention to treat hydrogen lean carbon containing feeds and hydrogen rich carbon containing feeds. Generally, the hydrocarbonaceous feed can be hydropyrolyzed to olefins and aromatic compounds or to a hydrocarbonaceous stream that is capable of being further processed to olefins and aromatic compounds. When a hydrogen lean carbonaceous feed is used it is preferable to also use a hydrogen donor source of the present invention. The hydrogen donor source may be one or more hydrocarbons that react to provide hydrogen atoms to one or more compounds in the hydrogen lean carbonaceous feed. Non-limiting examples of single stage (FIG. 1) and multi-stage processes (FIG. 2) are provided below.

(29) Referring to FIG. 1, FIG. 1 is a schematic of hydropyrolysis system 100 that includes a single stage reactor 102. Examples of reactors that can be used in the context of the present invention include fixed-bed reactors, stacked bed reactors, fluidized bed reactors, ebullating bed reactors, slurry reactors, rotating kiln reactors, continuously stirred tank reactors, spray reactors, or liquid/liquid contactors. The hydrogen lean carbon containing feed (for example, wood having a hydrogen content of 6 wt. % to 7 wt. %) enters the single stage reactor 102 via a hydrogen lean carbon containing feed inlet 104. Hydropyrolysis of a hydrogen lean carbon containing feed or a hydrogen rich carbon containing feed in system 100 may be a continuous process or a batch process. In some embodiments, the single stage reactor 102 can also include one or more catalysts (for example, two catalysts). Non-limiting examples of catalysts that can be used in the context of the present invention are provided throughout this specification. The system 100 can also include a hydrogen donor feed inlet 106 to transfer a hydrogen donor feed (for example, a virgin polymer, a waste polymer, or mixtures thereof) into the single stage reactor 102. Alternatively, the hydrogen lean carbon containing feed and the hydrogen donor feed streams can be simultaneously placed into the reactor 102 via a single inlet 104 or 106 such that the hydrogen lean carbon containing feed is mixed with the hydrogen donor feed and enters the reactor 102 as a one stream mixture. Still further, the system 100 can be configured to have the hydrogen lean carbon containing feed enter the reactor 102 downstream from the entrance of the hydrogen donor feed. Alternatively, the system 100 can be configured to have the hydrogen lean carbon containing feed enter the reactor 102 upstream from the entrance of the hydrogen donor feed. In still other embodiments, the system 100 can be configured to have the hydrogen lean carbon containing feed and the hydrogen donor feed enter the reactor 102 at approximately the same time and position in the reactor 102 relative to one another. By way of example only, in certain instances, it may be advantageous to have a very deficient hydrogen carbon containing feed (e.g., less than 6 weight percent of hydrogen content in the feed) to enter downstream of the hydrogen donor feed to allow time for the hydrogen donor feed to generate hydrogen for the hydrogen lean carbon containing feed. By comparison, it may be more advantageous to have a hydrogen lean carbon containing feed having a hydrogen content of 6 wt. % or more to enter simultaneously with the hydrogen donor feed to allow for less reaction time with the hydrogen donor feed. In any instance, the placement of the inlets 104 and 106 can be positioned to achieve a desired result. Once the reaction between the hydrogen lean carbon containing feed and the hydrogen donor feed takes place, the product (e.g., olefins, aromatic compounds, or hydrocarbonaceous stream, or mixtures thereof) can exit the reactor 102 via an outlet 108. In the reactor 102, hydrogen gas (H.sub.2) can be generated via the reaction process and removed from the product via separation unit 110. Separation unit 110 may be any known separation unit capable of separating hydrogen gas from hydrocarbons, for example, a membrane separation unit, or gas/liquid separation unit. If desired, the produced hydrogen gas and/or any gaseous hydrocarbons can then be recycled by adding it to the hydrogen donor feed via a conduit 112. The recycled hydrogen gas can be used to reduce coke formation in the reactor 102 or manage coke lay down on the catalyst.

(30) Referring to FIG. 2, FIG. 2 is a schematic of a multi-stage system 200 that can include a reactor 102 (such as that used in the single-stage system 100) and at least a second reactor 202. The second reactor 202 can be the type of reactor as 102 or can be a different type of reactor than 102. Non-limiting examples of reactors that can be used for the reactor 202 include fixed-bed reactors, stacked bed reactors, fluidized bed reactors, ebullating bed reactors, slurry reactors, rotating kiln reactors, continuously stirred tank reactors, spray reactors, or liquid/liquid contactors. When the product produced in reactor 102 includes a mixture of olefins, aromatics, and other compounds, it can exit the outlet 108 and then be further processed in reactor 202 to further convert the other compounds into olefins and aromatics. Non-limiting examples of these other compounds can include paraffins or naphthenes. Alternatively, the second reactor 202 can process the olefins and aromatics into additional downstream products that are desired in the chemical industry. Non-limiting examples of the further processing of olefins (e.g., ethylene, propylene) and aromatics (e.g., benzene, toluene, xylenes) is provided in FIGS. 3A-3E. Still further, when the product produced in reactor 102 includes a hydrocarbonaceous stream, the product can exit the outlet 108 and then be further processed in reactor 202 to further convert the hydrocarbonaceous stream into olefins and aromatics. Still further, and while not illustrated, it is contemplated that additional reactors can be added to the multi-stage system 200 so as to produce a desired end product. Alternatively, intermediate products can be isolated and used in other reactor systems to produce a desired end product. In either instance, an outlet 204 can be used to isolate or collect the produced intermediate or end products. Also, the system 200 can be set up such that 102 and 202 are separate or different stages or positions in the same reactor.

(31) In still other embodiments of the present invention, it is contemplated that multiple hydrogen lean carbon containing feeds can be processed at the same time. For instance, one hydrogen lean carbon containing feed could include a biomass (e.g., wood) while the other could include bio oil. In such instances, it may be that the different streams would have different amounts of hydrogen content. Therefore, the stream having less hydrogen content could benefit from a longer contact time with a hydrogen donor stream than the stream having more hydrogen content. Therefore, the inlets for each hydrogen lean carbon containing feed can be positioned relative to the inlet for the hydrogen donor feed. By way of example, FIG. 4 depicts a schematic of a single stage system 300 that includes a rector 102 with multiple inlets. A hydrogen donor feed can enter the reactor 102 via inlet 106. The dashed arrow 118 depicts the flow of hydrogen donor feed stream through the reactor 102. A first hydrogen lean carbon containing feed can be introduced into via inlet 104, while a second hydrogen lean carbon containing feed can be introduced via inlet 120, which is placed downstream from inlet 104. In this set up, the first hydrogen lean carbon containing feed can have less hydrogen content than the second stream. By placing inlet 104 upstream from inlet 120, the first hydrogen lean carbon containing feed can have a longer contact time with the hydrogen donor stream, while the second hydrogen lean carbon containing feed can have a shorter contact time with the hydrogen donor stream. This allows for two different hydrogen lean carbon streams to be processed at the same time to maximize the olefin or aromatic production or to maximize the production of a carbonaceous stream that is further processed into olefins or aromatics. In some instances, the inlets 104 and 120 are positioned at the same location in the reactor 102; however, the positioning of the inlets as shown in FIG. 4 is preferred. In some instances, the introduction of feed through the inlets 104 and 120 is automated to allow feed to be provided to the reactor 102 based on the composition of the stream exiting outlet 108. In a non-limiting example, the inlets 104 and 120 and/or the outlet 108 can be equipped with an electronic control system and/or analysis equipment to monitor the composition of the hydrocarbonaceous mixture exiting the outlet 108 and provide electronic communication to valves associated with the inlets 104 and 120 to operate the valves (for example, open or close the valves) in response to the composition of exiting mixture.

(32) In still other embodiments, the hydrogen donor stream can include a nitrogen containing compound, for example, ammonia or urea compounds. In such embodiments, the ammonia or urea hydrogen donor stream can be introduced upstream of the reactor 102. FIG. 5 depicts a schematic of a system 400 that includes an ammonia or urea hydrogen donor feed. The reactor in this system 400 includes a first stage 124 and a second stage 102. A urea or ammonia stream can enter the first stage 124 via inlet 122. Stage 124 can include a catalyst that is capable of converting the ammonia or urea to hydrogen gas. For example, the catalyst may be a nickel-tungsten type catalyst. The ammonia and/or urea are contacted with the catalyst in stage 124 at temperatures sufficient to convert the ammonia and/or urea to a gas stream comprising hydrogen gas, nitrogen, and water. The gas stream can flow into stage 102 as shown by dashed arrow 126. A hydrogen lean carbon stream can be introduced into the second stage 102 via inlet 104, thereby contacting the hydrogen gas containing stream 126 to generate desired products (e.g., olefins, aromatics, carbonaceous stream that can be further processed into olefins and aromatics). This set-up allows for different processing conditions within the first 124 and second 102 stages of a reactor. In some embodiments, however, stage 124 and stage 102 can be separate reactors.

(33) C. Processing Conditions

(34) The reaction processing conditions in the reactor 102 or the reactor 202, or both, can be varied to achieve a desired result (e.g., olefin product, aromatic production, hydrocarbonaceous product that can be further converted into olefins or aromatics, etc.). In one non-limiting aspect, the hydrogen lean carbon containing feed can be contacted with a catalyst (or a mixture of catalysts) in the presence of a hydrogen donor feed to produce olefins, aromatics, or hydrocarbonaceous products to be further processed into olefins and aromatics. The processing conditions include temperature, pressure, hydrogen donor flow, hydrogen lean carbon containing feed flow, hydrogen rich carbon containing feed flow, or any combination thereof. Processing conditions are controlled, in some instances, to produce products with specific properties. Temperature may range from about 400 C. to about 750 C., from about 450 C. to about 700 C., or from about 500 C. to about 650 C. Pressures may range from about 0.1 megapascal (MPa) to about 20 MPa, from about 1 MPa to about 15 MPa, or from about 5 MPa to about 10 MPa. Weight hourly space velocity (WHSV) for the hydrogen lean carbon containing feed or the hydrogen rich carbon containing feed can be from 0.01 to about 10 h.sup.1. WHSV for the hydrogen donor feed can range from 0.01 to about 10 h.sup.1. In some embodiments, a carrier gas may be combined with the hydrogen donor feed and recirculated through the stages. Non-limiting carrier gases include nitrogen, helium, argon, steam, hydrocarbon rich product gas generated in the process, hydrocarbon gas having one or more of C.sub.1 to C.sub.4 carbon compounds. In some embodiments, the carrier gas includes 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% or any range there between, by volume or mole, of hydrogen gas and the 95% to 85%, by volume, of nitrogen gas, helium gas, or argon gas, steam, hydrocarbon gas having one or more of C.sub.1 to C.sub.4 carbon compounds, or any combination thereof. The carrier gas may enhance mixing in the stage. In some instances steam can be used as a carrier gas in a once-through mode. In other instances, a combination of steam and carrier gases can be used with condensation of steam in the reactor downstream section. Most preferred carrier gases are steam and hydrocarbon product gas to facilitate reactor downstream product condensation. In one aspect, a carrier gas stream includes lift or acceleration gas if a fluidized bed reactor is used. Carrier gas stream can also include any gases used in aiding transfer of solid feed to reactor or any other gases entering the reaction zone. The process conditions may be adjusted depending on the hydrocarbonaceous feed used and the product distribution or slate of desired products. Severity of the process conditions may be manipulated by changing, the hydrogen donor feed, pressure, flow rates of various feed streams and/or carrier streams, the temperature of the process, and, if a catalyst is used, the catalyst type and/or catalyst to feed ratio, feed or carrier gas pre-heat temperature, atomization of liquid feed to result in smaller droplets, contact time, or combinations thereof.

(35) D. Catalysts and Reaction Products

(36) In some embodiments, one or more catalysts or a mixture of catalysts are used in the processes of the present invention. The catalysts can be capable of catalytic cracking of large molecules and hydrogenation/dehydrogenation of compounds in the feed to produce a product that includes olefins and aromatics compounds, or a hydrocarbonaceous stream that is processed into olefins and aromatic compounds. The catalyst or mixture of catalyst may be chosen depending on the type of feed and quality of feed stock to be processed. Contacting the hydrocarbon feeds alone or in the presence of a hydrogen donor feed with the catalyst can result in the addition of hydrogen to hydrogen deficient compounds and cracking of large molecules to smaller molecules. Examples of addition of hydrogen to hydrogen deficient compounds includes, but are not limited to, saturation of aromatic compounds, saturation of olefins, opening of cyclic compounds, or any combination thereof. Cracking of large molecules to smaller molecules may produce a product that includes olefins and aromatic compounds or a hydrocarbonaceous stream that may be further processed into olefins and aromatic compounds. In some embodiments, the catalyst is capable of reforming carbonaceous compounds into aromatics.

(37) In addition to hydrogenation and cracking of the compounds in the hydrocarbon feed stream, the following reactions may occur: (a) removal of side chains present on mono-aromatic compounds present in the un-cracked or cracked hydrogenated feed; (b) aromatization of paraffins, olefins, or naphthenes present in the un-cracked or cracked hydrogenated feed; (c) hydrogenation of coke or minimization of coke formation; (d) isomerization of compounds present in the un-cracked or cracked hydrogenated feed; (e) hydrodeoxygenation of compounds present in the un-cracked or cracked hydrogenated feed to aromatics (f) desulfurization of compounds and (g) denitrogenation of compounds, or any combination of (a) through (g). These reactions may occur in a single stage or positioned downstream of the stage. The same catalyst used for hydropyrolysis may be used to catalyze these reactions. In some embodiments, different catalysts are selected depending on the product produced after hydropyrolysis. The catalyst to facilitate the additional reactions may be positioned in a stage or reactor downstream of the stage or reactor where hydropyrolysis is being performed.

(38) Catalysts used for the processes described herein may be supported or unsupported catalysts. The support may be active or inactive. The support may include, but is not limited to, silica, alumina, carbon titania, zirconia, zeolite, or any combination thereof. All of the support materials can be purchased or be made by processes known to those of ordinary skill in the art (e.g., precipitation/co-precipitation, sol-gel, templates/surface derivatized metal oxides synthesis, solid-state synthesis, of mixed metal oxides, microemulsion technique, solvothermal, sonochemical, combustion synthesis, etc.).

(39) One or more of the catalysts may include one or more metals or one or more metal compounds. One or more metals or metal compounds thereof include transition metals. Supported catalyst may be prepared using generally known catalyst preparation techniques. In some embodiments, the support may be impregnated with metal to form a catalyst. Impregnation aids may or may not be used during preparation of the catalyst. Wet impregnation of supports may load the catalyst with one or more metals or compounds thereof. The impregnation may be repeated multiple times to add (load) different metals or metal compounds to the support or load the same metal on the catalyst in a step-wise manner.

(40) In some embodiments, one or more of the catalysts includes one or more noble metals. Noble metals include, but are not limited to, ruthenium, rhodium palladium, platinum, silver, osmium, iridium, or any combination thereof. In some embodiments, the catalyst includes a noble metal or noble metal compound thereof, a metal from Group VIB or metal compound thereof, a non-noble Group VIII metal or a non-noble metal compound thereof, or any combination thereof. Group VIB metals include chromium, molybdenum and tungsten. Non-noble Group VIII metals include, iron, cobalt, nickel, or any combination thereof. In some embodiments, one catalyst will include a noble metal or noble metal compound and a second catalyst will include a Group VIB metal or a metal compound thereof. Specific compounds are disclosed above and throughout this specification. These compounds are commercially available from a wide range of sources (e.g., Sigma-Aldrich Co. LLC (St. Louis, Mo., USA); Alfa Aesar GmbH & Co KG, A Johnson Matthey Company (Germany)). Catalysts described herein may be synthesized or be commercially obtained.

(41) In some embodiments, a FCC catalyst is used to treat the hydrocarbonaceous feeds and/or the hydrocarbonaceous streams generated from treating the hydrocarbonaceous feeds. The FCC catalyst may be mixed with other catalyst or used in one or more stages. A FCC catalyst may include a X-type zeolite, a Y-type or USY-type zeolite, mordenite, faujasite, nano-crystalline zeolites, MCM mesoporous materials, SBA-15, a silico-alumino phosphate, a gallophosphate, a titanophosphate, a spent FCC catalyst, or any combination thereof. The FCC catalyst may include a naturally occurring metal or a metal that has been embedded in an active or in-active matrix. A zeolite includes, but is not limited to, ZSM-5, ZSM-11, aluminosilicate zeolite, ferrierite, heulandite, zeolite A, erionite, chabazite and any combination thereof. Zeolites are well known in the art and can be commercially obtained or synthesized (See, Singh and Dutta (2003) in Handbook of zeolite science and technology, eds. Auerbach et al. pp. 21-64).

(42) In some embodiments, the HDO catalyst is used to treat the hydrocarbonaceous feeds or the olefins, aromatics, and/or the hydrocarbonaceous streams generated from treating the hydrocarbonaceous feeds. The HDO catalyst may be mixed with one or more of the catalyst used for hydropyrolysis or used in a stage downstream of the hydropyrolysis stage. The HDO catalyst hydrogenates and deoxygenates one of more oxygen compounds in the hydrocarbonaceous feeds. The HDO catalyst may include one or more metals, one or more metal compounds thereof on a support. The metal or metal compound thereof may be from Group VIB and/or Group VIII. At least one of the metal or metal compounds thereof used in a HDO catalyst include molybdenum, cobalt, nickel, iron, platinum, palladium, and any combination thereof. The metals or metal compounds thereof may be used alone or together. For example, the HDO catalyst may include cobalt and molybdenum, nickel and molybdenum, iron and molybdenum, palladium and molybdenum, platinum and molybdenum, or nickel and platinum. In some embodiments, the HDO catalyst also includes one or more zeolites or metal loaded zeolites. For example, the HDO catalyst may be mixed with a ZSM-5 catalyst or a metal loaded ZSM-5 catalyst.

(43) In some aspects of the invention, a desulfurization and/or denitrogenation catalysts is used to remove nitrogen and sulfur from hydrocarbonaceous compounds. Non-limiting examples of desulfurization and/or denitrogenation catalysts include Co and Mo, Ni and Mo, W and Mo or other metal combinations on alumina. Catalyst currently available as pre-treatment catalysts for desulfurization and denitrogenation in hydrocracking processes, diesel hydrodesulphurization processes and vacuum gas oil hydrotreating processes can be used.

(44) In some embodiments, the hydrocracking catalyst is used to hydropyrolysis or hydrogenation and crack hydrocarbonaceous compounds. The hydrocracking or hydrogenation catalyst may also remove heteroatoms, for example, sulfur, nitrogen and/or oxygen from the hydrocarbonaceous compounds. The hydrocracking catalyst can include a Group VIB metal or a metal compound thereof, a Group VIII metal or metal compound thereof, or any combination thereof. The Group VIB metal or a compound thereof includes molybdenum and/or tungsten. The Group VIII metal or a compound thereof includes nickel and/or cobalt. Non-limiting examples of metals used in a hydrocracking catalyst, include cobalt-molybdenum catalyst, nickel-molybdenum catalyst, and tungsten-molybdenum catalyst. The hydrocracking catalyst may be subjected to a sulfiding source (for example, hydrogen sulfide) to convert any metals or metal oxides to metal sulfides prior to use. The hydrocracking catalyst is a metal sulfide on a support, or an unsupported metal sulfide catalyst. An example of an unsupported metal sulfide catalyst is a molybdenum sulfide. In some embodiments, the hydrocracking catalyst is a zeolite, or a mixture of the hydrocracking catalyst and one or more zeolites.

(45) The aromatization catalyst catalyzes the formation of aromatic compounds from paraffins, olefins or naphthenes. The aromatization catalyst may be mixed with other catalysts or used alone. For example, the aromatization catalyst is used in the hydropyrolysis stage or a stage downstream of the hydropyrolysis stage. In some embodiments, the aromatization catalyst includes a Group VIII noble metal or a metal compound thereof, a Group VIB metal or a metal compound thereof, tin or a tin compound, gallium or a gallium compound, or any combination thereof. The metal(s) may be supported on alumina, zeolites or any combination thereof. The aromatization catalyst may be mixed with a FCC catalyst. Non-limiting examples, of aromatization catalyst include platinum-molybdenum catalyst, tin-platinum catalyst, platinum-gallium catalyst, and platinum-chromium catalyst.

(46) In one non-limiting aspect, a catalyst-to-feed ratio of about 0.001 to about 20, about 0.01 to 15, or about 0.1 to about 10 based on the total feed may be used in the reactors of the system. In some embodiments, a slurry of the catalyst and crude feed may include from about 0.001 grams to 10 grams, about 0.005 to 5 grams, or about 0.01 to 3 grams of catalyst per 100 grams of lean hydrogen carbon containing feed in the stage(s) of the reactor.

(47) By way of example, the catalyst used in the processes of the present invention can include sand and at least one of a FCC catalyst, a zeolite catalyst, a hydrodeoxygenation (HDO) catalyst, a hydrocracking catalyst, an aromatization catalyst, a spent FCC catalyst, and any combination thereof. In one particular aspect of the invention, the catalyst is a spent fluidized catalytic cracking (FCC) catalyst mixed with a ZSM5 zeolite catalyst in a weight ratio of FCC:ZSM-5 of 3:1, 2.9:1, 2.8:1, 2.7:1, 2.6:1, 2.5:1, 2.4:1, 2.3:1, 2.2:1, 2.1:1, 2:1 1.8:1, 1.7:1, 1.5:1, 1:1 or any range there between. The catalyst can include 75 to 50 wt. %, or 62.5 wt % of a spent FCC catalyst and 25 to 50 wt. %, or 37.5 wt. % of a ZSM-5 catalyst.

(48) E. Use of Sand With Catalysts

(49) In some embodiments of the present invention, sand can be mixed with a given catalyst. Non-limiting examples of sand include, quartz sand, silica sand, sand containing metal or metal oxide contaminants, or any combination thereof. The use of sand may inhibit fouling of the catalyst by contaminants produced during the hydropyrolysis. Incorporation of sand in the catalyst helps in altering the catalyst acidity and provides a method to balance the thermal and catalytic activities in a pyrolysis process. A mixture of catalyst and sand can be used at the same or higher temperature than with only catalysts without sand used for the same conversion. Inclusion of sand with the catalyst may alter degradation properties as compared to using 100 wt. % sand. The amount of sand that can be used up to 99 wt. % based on the total amount of sand/catalyst mixture. Preferably up to 25 wt. % sand based on the total weight of the sand and catalyst combination can be used. In some embodiments, contact of a hydrocarbonaceous feed with a catalyst containing sand produces a product enriched in ethylene. In such a process, a ratio of ethylene to propylene may be increased by mixing sand with the catalyst. It was discovered that sand can be used in amounts of up to 25 wt. % of the total amount of the sand/catalyst mixture to increase the ethylene to propylene ratio without appreciable drop in yields of high value light gas olefins and aromatics.

(50) By way of example, the catalyst used in the processes of the present invention can include sand and at least one of a FCC catalyst, a zeolite catalyst, a hydrodeoxygenation (HDO) catalyst, a hydrocracking catalyst, an aromatization catalyst, a spent FCC catalyst, and any combination thereof. For example, the catalyst may be a mixture of sand, a metal loaded spent FCC catalyst and a metal loaded ZSM-5 catalyst. In some embodiments, a catalyst contains sand, a spent FCC catalyst and a ZSM-5 catalyst. In some embodiments, the catalyst are integrated particles that include sand, a metal loaded FCC catalyst, a zeolite, a spent FCC catalyst and any combination thereof embedded in an active matrix, wherein the catalyst is capable of catalyzing cracking, aromatization, hydrogenation and dehydrogenation reactions. The catalyst may include a mixture of a metal loaded fluidized catalytic cracking (FCC) and a metal loaded ZSM-5 catalyst. In some instances, the catalyst may not contain sand and contains at least one of the above-catalysts.

EXAMPLES

(51) The present invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes only, and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of noncritical parameters which can be changed or modified to yield essentially the same results.

Example 1

Conversion of Hydrogen Lean Carbon Containing Feeds

(52) Different mixtures of hydrogen lean carbon containing feeds (wood powder and high density polyethylene powder (HDPE, 200 microns particle size)) were pyrolyzed in a lab reactor using the conditions in Table 1 using nitrogen as carrier gas at a flow rate of 175 normal cc/min (Ncc/min). No hydrogen containing gas was introduced into the reactor and the operating pressure was atmospheric. The reactor was an in-situ fluidized bed tubular reactor having a length of 783 mm and an inner diameter of 15 mm, and was housed in a split-zone 3-zone tubular furnace with independent temperature control for each zone. The size of each zone was 9.3 inches (236.2 mm). The overall heated length of the reactor placed inside the furnace was 591 mm. The reactor wall temperature was measured at the center of each zone and was used to control the heating of each furnace zone. The reactor had a conical bottom and the reactor bed temperature was measured using a thermocouple housed inside a thermowell and placed inside the reactor at the top of the conical bottom. Also, the reactor wall temperature was measured at the conical bottom to ensure that the bottom of the reactor was hot. The reactor bottom was placed at the middle of the furnace bottom zone for minimizing the effect of furnace end cap heat losses and maintaining the reactor bottom wall temperature within a difference of 20 C. of the internal bed temperature measured. In Table 1, gas produced (make) from wood alone was calculated as follows:
Gas produced from wood=(Gas yield with mixed feed(gas yield from pure HDPEweight fraction of HDPE in feed))/weight fraction of wood in feed.

(53) Light olefin gas produced from wood alone was calculated using the formula of:
Light olefin gas produced from wood=(light olefin gas yield with mixed feed(light olefin gas yield from pure HDPEweight fraction of HDPE in feed))/weight fraction of wood in feed.

(54) Coke produced from wood alone is calculated using the formula of:
Coke produced from wood=(coke yield with mixed feed(coke yield from pure HDPEweight fraction of HDPE in feed))/weight fraction of wood in feed.

(55) Catalyst A was spent FCC catalyst (62.50%)+ZSM-5 zeolite catalyst (37.5%). Catalyst B was spent FCC catalyst (75%)+ZSM-5 Zeolite catalyst (25%).

(56) TABLE-US-00001 TABLE 1 Feed type Solid Powder Solid Powder Solid Powder Solid Powder Feed name HDPE 82% HDPE + 50% HDPE + 20% HDPE + 18% Wood 50% Wood 80% Wood Catalyst name A B A A C/F ratio, gm/gm 6.01 5.98 9.02 5.96 Reaction temperature at start, C. 700 620 670 670 Feed weight transferred, gm 1.50 0.75 0.75 1.50 Coke yield, wt. % 1.85 4.87 10.38 22.52 wt. % H.sub.2, C.sub.1-C.sub.4 yield on 54.92 38.89 31.38 18.64 normalized products Gas make contribution from wood 34.11 7.84 9.57 alone based on removal of contribution from HDPE Total Light gas olefins yield, wt. % 41.01 29.52 21.60 8.67 Light olefins make contribution 22.81 2.19 0.58 from wood alone based on removal of contribution from HDPE, wt. % Total gas saturates, wt. % 11.48 6.79 3.81 1.65 C.sub.2=/C.sub.2sat, wt/wt 8.94 7.74 7.12 3.56 C.sub.3=/C.sub.3sat, wt/wt 4.60 5.87 6.51 5.50 C.sub.4=/C.sub.4sat, wt/wt 2.24 3.10 4.53 6.80 Hydrogen Transfer Index (HTI) 0.58 0.47 0.33 0.31 Coke make contribution from 18.63 18.90 27.69 wood alone based on removal of contribution from HDPE, wt. %

(57) As can be seen from Table 1, the gas produced from wood alone decreases when the plastic content was increased from 20% to 50%, however, the yield of light olefins alone from wood increases up to a plastic content of 50% in feed and decreases after that. Cracking of plastic feed was observed to be faster than cracking of biomass. Less coking was observed during cracking of the plastic feed as compared to the biomass cracking process. Coke deposition during biomass cracking reduced the activity of catalyst as compared to the plastic cracking process. When plastic feed rich streams (82% plastic) are used in the mixture, the yield of gases from the mixture decreased as compared to mixtures having less than 50 wt. % plastic. Thus, the amount of gases and olefins produced may be adjusted based on the amount of hydrogen donor feed present in the mixture. The calculated coke produced for wood, only when the mixture of wood and plastic feed was pyrolyzed, demonstrated that with increasing amount of plastic in feed, the coke produced from wood alone was reduced. The hydrogen transfer index (HTI) for each of the reactions were determined from the ratio of (propane+butane yields)/propylene yields, and are listed in Table 1. It can be concluded from the hydrogen transfer index that as the plastic content in the feed was increased the product gases become saturated (hydrogen donor). Based on the above, it can also be concluded that recycle of H.sub.2 rich gases and operating at higher pressures can improve the hydropyrolysis process.

Example 2

Conversion of Hydrogen Rich Carbon Containing Feeds

(58) Treatment of a hydrogen rich carbon containing stream was performed using catalysts that included 0 wt. % sand, 25 wt. % sand, 50% sand and 100 wt. % sand. The catalyst having 50 wt. % sand was prepared by mixing 50 wt. % of pure silica sand (99% pure) with 50 wt. % of Catalyst A (Example 1, 62.5 wt. % spent FCC catalyst and 37.5 wt. % of ZSM-5 catalyst). The catalyst having 25 wt. % sand was prepared by mixing 25 wt. % of pure silica sand (99% pure) with 75 wt. % of Catalyst A (Example 1, 62.5 wt. % spent FCC catalyst and 37.5 wt. % of ZSM-5 catalyst). The catalyst having 0 wt. % sand was 100 wt. % Catalyst A (i.e., 62.5 wt. % spent FCC catalyst and 37.5 wt. % of ZSM-5 catalyst. Catalyst and powdered hydrogen rich carbon containing feed (mixed plastic and/or thermal polymers) was added to the reactor. The reactor was the same as the reactor described in Example 1. The plastic feed was in the form of a 200 micron plastic powder. The mixed plastic feed used in these experiments is listed in Table 2.

(59) TABLE-US-00002 TABLE 2 Material Amount HDPE 19 wt. % Low Density Polyethylene (LDPE) 21 wt. % Polypropylene (PP) 24 wt. % C.sub.4-LLDPE 12 wt. % C.sub.6-Linear Low Density Polyethylene (LLDPE) 6 wt. % Polystyrene (PS) 11 wt. % Polyethylene terephthalate (PET) 7 wt. %

(60) The FCC catalyst was a spent FCC catalyst obtained from an operating refinery. The FCC spent catalyst contained 0.23 wt. % residual coke. The ZSM-5 zeolite catalyst used was a commercially available ZSM-5 zeolite catalyst. The plastic feed was mixed with the catalyst containing sand by swirling in a cup and then fed into the reactor. A flow of N.sub.2 gas at 175 Ncc/min was used as a fluidizing and carrier gas. Catalyst and powdered hydrogen rich carbon containing feed (mixed plastic) was added to the reactor after the reactor attained a temperature of about 700 C. under atmospheric conditions. Immediately after feed and catalyst mixture were added, products evolved out of the reactor and were collected for 10 minutes. Most of these products evolved in the first 2-3 minutes. The catalyst to feed ratio was 6.0. The conversion products from the reactor were collected and condensed in a condenser. The uncondensed products were collected in a gas collection vessel and the gas composition was analyzed using a refinery gas analyzer (M/s AC Analyticals B.V., The Netherlands). Liquid products were characterized for their boiling point distribution using a simulated distillation GC (M/s AC Analyticals B.V., The Netherlands). In addition a detailed hydrocarbon analysis (up to C.sub.13 hydrocarbons) was carried out using a DHA analyzer (M/s AC Analyticals B.V., The Netherlands). The coke deposited on the catalyst was determined using an IR-based CO and CO.sub.2 analyzer. The mass balances were determined by summing the yields of gas, liquid and coke. Individual product yields were determined and reported on a normalized product basis.

(61) Table 3A lists the percentages of light gas olefins and yields of aromatics, liquid olefins, iso-paraffins, n-paraffins, and naphthenes boiling below 240 C. for 0 wt. % sand, 25 wt. % sand, and 100 wt. % sand, respectively. FIG. 6 is a graphical representation of the wt. % of methane and ethylene versus wt. % sand in the catalyst. As shown in FIG. 6 and Table 3B, the amount of ethylene and methane increased as the amount of sand was increased in the mixture indicating more thermal cracking with increasing sand content. Table 4 lists the reaction conditions and percentages of C.sub.2, C.sub.3, and C.sub.4 olefins for 0 wt. % sand, 25 wt. % sand, 50 wt. % sand, and 100 wt. % sand, respectively. FIG. 7 is a graphical representation of the wt. % of C.sub.2, C.sub.3, and C.sub.4 olefins versus wt. % sand in the catalyst. As shown in FIG. 7 and Table 4, the percentage yields of light gas olefin decreased when 50 wt. % or more of sand was used. This indicates that the catalytic activity of the catalyst mixture is reduced for making light gas C.sub.3 and C.sub.4 olefins. Table 5 lists the reaction conditions and percentages of heavies for 0 wt. % sand, 25 wt. % sand, 50 wt. % sand, and 100 wt. % sand, respectively. FIG. 8 is a graphical representation of wt. % of heavies (hydrocarbons having a boiling point of 3700 C. or more), versus wt. % sand in the catalyst. As shown in FIG. 8 and Table 5, the percentage of heavies decreased when 50 wt. % or more of sand was used. Table 6 lists the reaction conditions and percentages of coke for 0 wt. % sand, 25 wt. % sand, 50 wt. % sand, and 100 wt. % sand, respectively. FIG. 9 is a graphical representation of wt. % of total olefins versus wt. % sand in the catalyst mixture. As shown in FIG. 9 and Table 6 the total light gas olefins yield decreased when 50 wt. % or more of sand was used. Table 5 lists the reaction conditions and percentages of total gas olefins for 0 wt. % sand, 25 wt. % sand, 50 wt. % sand, and 100 wt. % sand, respectively. FIG. 10 is a graphical representation of wt. % of coke versus wt. % sand in the catalyst mixture. As shown in FIG. 10 and Table 6, the percentage of coke yield increased when 50 wt. % or more of sand was used. Table 7 lists the feed composition, catalyst composition, and reactor bed temperatures of total olefins in the gaseous hydrocarbon stream for 0 wt. % sand, 25 wt. % sand, 50 wt. % sand, and 100 wt. % sand, respectively. FIG. 11 is a graphical representation of wt. % of olefins in a gas stream containing hydrogen gas and C.sub.4 or less hydrocarbons versus wt. % sand in the catalyst mixture. As shown in FIG. 11 and Table 7, the amount of olefins in the gaseous stream decreases when 50 wt. % or more of sand is used. FIGS. 12-16 are other graphical representations of products (e.g., aromatics, olefins, paraffins, iso-paraffins, naphthenes, etc.) obtained from using sand in combination with a mixture of catalysts. FIG. 12 is a graphical representation of wt. % of aromatics versus wt. % sand in the catalyst mixture. As shown in FIG. 12, a slight decrease in aromatics yield was observed when 50 wt. % or more of sand was use. FIG. 13 is a graphical representation of wt. % of paraffins versus wt. % sand in the catalyst mixture. FIG. 14 is a graphical representation of wt. % of iso-paraffins versus wt. % sand in the catalyst mixture. As shown in FIGS. 13-14, a substantial decrease in the paraffins and iso-paraffins yield was observed when 25 wt. % or more of sand was use. FIG. 15 is a graphical representation of wt. % of napthenes versus wt. % sand in the catalyst mixture. As shown in FIG. 15, an increase in the naphthenes yield was observed when 20 wt. % or more of sand was used. FIG. 16 is a graphical representation of wt. % of liquid olefins versus wt. % sand in the catalyst mixture. As shown in FIG. 16, an increase in the liquid olefins yield was observed as the amount of sand was increased. As shown, in FIGS. 12-16, the amounts and/or types of compounds produced can be varied based on the amount of sand used in combination with the catalysts. Table 8 lists the reaction conditions and catalysts for 0 wt. % sand, 25 wt. % sand, 50 wt. % sand, and 100 wt. % sand, respectively. FIG. 17 is a graphical representation of the reaction bed temperature versus elapsed time after the feed was charged.

(62) These data show that the direct hydropyrolysis of a hydrogen rich carbon containing feed in the absence of a hydrogen donor feed results in a product that has more than 50 wt. % of olefins and aromatics. Further, mixing of sand in the catalyst in amounts of up to 25 wt. % results in (1) no loss of catalytic activity (i.e., olefin and aromatic yields are maintained), (2) a reduction in methane yield as compared to the use of sand alone, (3) increases the production of ethylene over propylene, and (d) reduces liquid isoparaffins and heavies.

(63) TABLE-US-00003 TABLE 3A Catalyst C.sub.2-C.sub.4 Liquid Iso- n- (wt. % Olefins Aromatics Olefins paraffins paraffins Naphthenes sand) wt. % wt. % wt. % wt. % wt. % wt. % 0 34.9 34.1 1.0 6.3 0.6 1.6 25 34.8 33.5 1.9 6.0 0.7 1.5 100 29.0 28.2 3.5 2.3 0.6 11.7

(64) TABLE-US-00004 TABLE 3B Catalyst Composition 0% 25% 50% 100% sand sand sand sand C/F ratio g/g 6.0 6.0 6.0 6.0 Reaction temperature 700 700 700 700 at start C. 1 Min. average reaction 603.4 583.8 557.8 518.4 bed temperature C. Dry catalyst fed g 8.9 9.0 9.0 9.0 Feed weight trans- 1.5 1.5 1.5 1.5 ferred g Methane yield, wt. % 1.5 2.0 3.4 6.4 Ethylene Yield, wt. % 6.8 7.1 7.5 10.3

(65) TABLE-US-00005 TABLE 4 Catalyst Composition, wt. % 0% 25% 50% 100% sand sand sand sand C/F ratio g/g 6.0 6.0 6.0 6.0 Reaction temperature 700 700 700 700 at start C. 1 Min average reaction 603.4 583.8 557.8 518.4 bed temperature C. Dry catalyst fed g 8.9 9.0 9.0 9.0 Feed weight trans- 1.5 1.5 1.5 1.5 ferred g C4 olefin, wt. % 12.3 12.0 11.6 7.8 C3 olefin, wt. % 15.8 15.8 15.4 10.9 C2 olefin, wt. % 6.8 7.1 7.5 10.3

(66) TABLE-US-00006 TABLE 5 Catalyst Composition, wt. % 0% 25% 50% 100% sand sand sand sand C/F ratio g/g 6.0 6.0 6.0 6.0 Reaction temperature 700 700 700 700 at start C. 1 Min. average reaction 603.4 583.8 557.8 518.4 bed temperature C. Dry catalyst fed g 8.9 9.0 9.0 9.0 Feed weight trans- 1.5 1.5 1.5 1.5 ferred g Heavies >370 C. 1.0 0.8 0.7 0.3

(67) TABLE-US-00007 TABLE 6 Catalyst Composition, wt. % 0% 25% 50% 100% sand sand sand sand C/F ratio g/g 6.0 6.0 6.0 6.0 Reaction temperature 700 700 700 700 at start C. 1 min average reaction 603.4 583.8 557.8 518.4 bed temperature C. Dry catalyst fed g 8.9 9.0 9.0 9.0 Feed weight trans- 1.5 1.5 1.5 1.5 ferred g Coke, wt. % 3.1 3.9 4.5 5.4

(68) TABLE-US-00008 TABLE 7 Catalyst Composition 0% 25% 50% 100% sand sand sand sand C/F ratio g/g 6.0 6.0 6.0 6.0 Reaction temperature 700 700 700 700 at start C. 1 min average reaction 603.4 583.8 557.8 518.4 bed temperature C. Dry catalyst fed g 8.9 9.0 9.0 9.0 Feed weight trans- 1.5 1.5 1.5 1.5 ferred g % olefins/Total gases 75.6 75.3 73.8 65.2

(69) TABLE-US-00009 TABLE 8 Feed name 0 25 50 100 Feed type Solid Powder Solid Powder Solid Powder Solid Powder Feed Composition Mixed Plastic Mixed Plastic Mixed Plastic Mixed Plastic Catalyst Composition, wt. % 0% sand 25% sand 50% sand 100% sand 0 min bed temperature, C. 700 700 700 700 10 sec bed temperature, C. 494 485 469 449 20 sec bed temperature, C. 569 498 489 463 40 sec bed temperature, C. 619 607 525 473 1 min bed temperature, C. 635 629 606 507 2 min bed temperature, C. 669 665 659 650 3 min bed temperature, C. 693 691 689 684 4 min bed temperature, C. 705 706 705 704 5 min bed temperature, C. 711 714 714 713 6 min bed temperature, C. 712 715 717 717 7 min bed temperature, C. 711 714 717 717 8 min bed temperature, C. 708 712 714 716 9 min bed temperature, C. 704 710 711 712 10 min bed temperature, C. 703 706 708 709 10 min Average, C. 666.6 660.9 651.6 636.7 1 min Average, C. 603.4 583.8 557.8 518.4

Example 3

Conversion of Hydrogen Rich Carbon Containing Feeds in the Presence of Carrier Gas Having Hydrogen to Inhibit Coking of Catalyst at High Temperatures

(70) Treatment of a hydrogen rich carbon containing stream was performed using Catalyst A in the presence and absence of hydrogen gas at various temperatures to determine the effect of a small amount of hydrogen to inhibit coking and maintain the activity of the catalyst. Mixed plastic (1.5 g) having the composition listed in Table 2 was mixed with Catalyst A (9 g, 62.5 wt. % spent FCC catalyst and 37.5 wt. % ZSM-5 zeolite catalyst). The combined mixture was then fed to the fluidized bed reactor described in Example 1. The plastic feed was in the form of a 200 micron plastic powder. A 10 mole or volume percent of H.sub.2 in N.sub.2 mixture was employed as the carrier gas at a flow rate of 175 NCC/min. Studies were conducted by maintaining the reactor bed temperature, before feed and catalyst mixture was introduced, at 600 C., 635 C. and 670 C. respectively (i.e. at 3 different starting temperatures). Studies were also conducted at the same conditions as before with 100% N.sub.2 as carrier gas. For each of the temperature condition studied, a new set of catalyst and feed mixture was prepared and used. Tables 9-14 summarize the experimental findings. Table 9 lists the reaction conditions and yields of products for each experiment. Table 10 lists the C.sub.1-C.sub.4 yield, % liquid yield and % coke yield for each experiment. Table 11 lists the total aromatics yield boiling below 240 C. in weight percent, the weight percentage yield of C.sub.6-C.sub.8 aromatics, the weight ratio of total aromatics yield to coke yield, the weight ratio of C.sub.6-C.sub.8 aromatics yield to coke yield, the weight ratio of light gas olefins yield to coke yield for each experiment. Table 12 lists the weight percentage yields of: C.sub.4 olefins, C.sub.3 olefin, C.sub.2 olefins, and total light gas olefins for each experiment. Table 13 lists the hydrogen transfer index (HTI), isomerization coefficient (defined as ratio of weigh percentage yield n-butane to yield of butene isomers), ratios of weight % yields of C.sub.2 olefin to C.sub.2 saturate, C.sub.3 olefin to C.sub.3 saturate, and C.sub.4 olefin to C.sub.4 saturate, and weight percentage of i-C.sub.4 in total C.sub.4 compounds, weight percentage concentration of olefins in total gases, and a ratio of wt. % light gas olefins to wt. % saturates yield for each experiment. Table 14 lists the detailed hydrocarbon analysis (DHA) of the liquid products and the balance of unknowns and heavies of the liquid products boiling below 240 C.

(71) From analysis of the data in Tables 10 and 11, a decrease in coke make at temperatures at 525 C. or above was observed when a small amount of hydrogen was present in the carrier gas. Thus, catalyst activity was improved at these temperatures when a small amount of hydrogen gas was introduced into the carrier gas to inhibit coke make on the catalyst. Also, the production of light gas olefins and aromatics increased slightly in presence of hydrogen gas. Since the ratios of light gas olefins yield per unit coke-make and the aromatics yield per unit coke-make were higher in the case when the carrier gas contained a small amount of hydrogen, it can be predicted that coke make can be reduced with a small amount of hydrogen gas present. Thus, the yields of light gas olefins and aromatics are predicted to be slightly higher in a circulating bed fluid catalytic cracking type unit operating on a constant regenerator air supply containing a small amount of hydrogen. By way of example, referring to the last two columns in Table 11, the ratios for light gas olefins to coke were 6.4 and 5.8 respectively. If a catalyst regenerator can handle about 5 wt % coke only, then that means for the case when the carrier gas contains a small amount of hydrogen, the light gas olefins yield at 5 wt % coke yield would be 32 wt % as compared to 29% yield of light gas olefins when the carrier gas did not contain any hydrogen. This means an increase in yield of light gas olefins by 3 wt %. Similar analysis on aromatics yield per unit coke would reveal an increase in aromatics yield in a circulating fluidized bed when the carrier gas contains small amount of hydrogen. Since production of light gas olefins and C.sub.6-C.sub.8 aromatics per unit amount of coke deposited and the total amount of aromatics was observed in the presence (Example 3) and absence of hydrogen gas (Example 2), it is believed that light gas olefins, total aromatics, in particular, C.sub.6-C.sub.8 aromatics can be produced when a hydrogen rich carbon stream is contacted with the catalyst of the present invention in a fluidized catalytic cracking unit.

(72) TABLE-US-00010 TABLE 9 10:90 10:90 10:90 Reaction Type H.sub.2:N.sub.2 100% N.sub.2 H.sub.2:N.sub.2 100% N.sub.2 H.sub.2:N.sub.2 100% N.sub.2 Feed name Mixed Mixed Mixed Mixed Mixed Mixed Plastic Plastic Plastic Plastic Plastic Plastic Catalyst name A A A A A A Feed weight transferred, gm 1.50 1.50 1.50 1.50 1.50 1.50 Bone Dry catalyst fed, gm 9.05 8.95 9.05 9.05 9.01 8.95 C/F ratio, gm/gm 6.03 6.0 6.03 6.03 6.00 6.0 Reaction temperature at 600 600 635 635 670 670 start, C. 1 min average reactor 482 472 525 525 567 570 bed temperature, C. Yields, wt. % on H.sub.2-free product basis Methane, wt. % 0.92 0.40 1.00 0.56 3.20 0.99 Ethane, wt. % 0.87 0.43 0.73 0.52 0.69 0.74 Ethylene, wt. % 6.17 3.68 6.50 5.07 6.36 5.78 Carbon dioxide, wt. % 1.29 1.63 1.54 1.93 1.85 1.91 Propane, wt. % 3.90 4.26 3.15 3.58 3.11 3.49 Propylene, wt. % 12.76 11.05 13.63 12.93 14.67 14.75 iso-Butane, wt. % 4.56 4.99 3.85 4.75 3.77 3.53 n-Butane, wt.% 2.67 1.84 2.07 1.57 1.31 1.41 trans-2-Butene, wt. % 3.16 2.67 3.10 2.89 2.99 3.01 1-Butene, wt. % 1.75 1.63 1.79 1.79 1.90 2.01 iso-Butylene, wt. % 4.68 4.55 4.56 4.76 4.72 4.97 cis-2-butene, wt. % 2.22 1.92 2.19 2.09 2.16 2.21 Carbon monoxide, wt. % 0.25 0.10 0.35 0.00 0.80 0.25 Gasoline, wt. % 43.83 45.34 41.66 42.42 42.11 43.30 Diesel, wt. % 5.75 9.14 7.55 8.37 4.73 5.16 Heavies, wt. % 0.56 1.64 0.78 0.88 0.49 0.86 Coke, wt. % 4.67 4.73 5.55 5.88 5.12 5.64

(73) TABLE-US-00011 TABLE 10 10:90 100% 10:90 100% 10:90 100% Reaction Type H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 C.sub.1-C.sub.4 yield, wt. % 45.2 39.1 44.5 42.5 47.5 45.0 % Liquid yield, wt. % 50.1 56.1 50.0 51.7 47.3 49.3 % Coke yield, wt. % 4.7 4.7 5.6 5.9 5.1 5.6

(74) TABLE-US-00012 TABLE 11 10:90 100% 10:90 100% 10:90 100% Reaction Type H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 Total aromatics yield 32.42 31.39 32.81 31.83 35.09 32.35 boiling below 240 C., wt. % C.sub.6-C.sub.8 aromatic, wt. % 23.81 23.20 24.44 22.63 26.33 22.87 Total Aromatics/Coke, Wt. ratio 6.9 6.6 5.9 5.4 6.9 5.7 (C.sub.6-C.sub.8 aromatics)/Coke, Wt. ratio 5.1 4.9 4.4 3.9 5.1 4.1 Light gas olefins/Coke, Wt. ratio 6.6 5.4 5.7 5.0 6.4 5.8

(75) TABLE-US-00013 TABLE 12 Reaction 10:90 100% 10:90 100% 10:90 100% Type H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 C.sub.4 olefins, 11.81 10.76 11.64 11.54 11.77 12.20 wt. % C.sub.3 olefin, 12.76 11.05 13.63 12.93 14.67 14.75 wt. % C.sub.2 olefin, 6.17 3.68 6.50 5.07 6.36 5.78 wt. % Total olefins, 30.74 25.49 31.77 29.54 32.80 32.72 wt. %

(76) TABLE-US-00014 TABLE 13 10:90 100% 10:90 100% 10:90 100% Reaction Type H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 Hydrogen 0.87 1.00 0.67 0.77 0.56 0.57 Transfer Index (HTI) Isomerization 0.174 0.178 0.182 0.184 0.192 0.197 coefficient C.sub.2 olefin/C.sub.2 7.1 8.6 8.9 9.8 9.2 7.9 saturate C.sub.3 olefin/C.sub.3 3.3 2.6 4.3 3.6 4.7 4.2 saturate C.sub.4 olefins/C.sub.4 1.6 1.6 2.0 1.8 2.3 2.5 saturates % of i-C.sub.4 in Total 23.9 28.4 21.9 26.6 22.4 20.6 C.sub.4 % of olefins in 68.0 65.1 71.5 69.6 69.0 72.6 Total gases % of olefins/ 2.6 2.2 3.2 2.8 3.7 3.6 % saturates

(77) TABLE-US-00015 TABLE 14 DHA Of Liquid Products Boiling Below 240 C. 10:90 100% 10:90 100% 10:90 100% Reaction Type H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 H.sub.2:N.sub.2 N.sub.2 Paraffins, wt. % 1.184 1.435 1.207 1.170 1.108 1.420 Isoparaffins, wt. % 10.161 12.389 9.598 12.120 8.545 13.330 Olefins, wt. % 2.944 9.159 2.555 4.858 0.976 3.900 Naphthenes, wt. % 3.727 5.390 3.135 3.867 2.329 4.030 Aromatics, wt. % 73.968 69.233 78.758 75.037 83.315 74.720 Balance Unknowns And Heavies BTX + EX content in liquid 54.32 51.17 58.67 53.35 62.52 52.81 boiling below 240 C., wt. %* *BTX-benzene, toluene, and xylenes; EB-ethyl benzene