System and process for the manufacture of hydrocarbons and upgraded coal by catalytic mild temperature pyrolysis of coal

Abstract

A process for upgrading a solid carbonaceous material includes heating the solid carbonaceous material in the presence of a catalyst under partial pyrolysis conditions and obtaining an upgraded solid carbonaceous product, a gaseous product, and a spent catalyst.

What is claimed is: 
     
         1 . A process for upgrading a solid carbonaceous material, comprising:
 heating the solid carbonaceous material in the presence of a catalyst under partial pyrolysis conditions, and   obtaining an upgraded solid carbonaceous product, a gaseous product, and a spent catalyst.   
     
     
         2 . The process of  claim 1 , wherein the solid carbonaceous material is coal and the upgraded solid carbonaceous product is an upgraded coal product. 
     
     
         3 . The process of  claim 1 , wherein a weight of fixed carbon retained in the upgraded solid carbonaceous product is at least 50 weight percent of fixed carbon in the solid carbonaceous material. 
     
     
         4 . The process of  claim 1 , wherein a weight of ash retained in the upgraded solid carbonaceous product is at least 60 weight percent of ash in the solid carbonaceous material. 
     
     
         5 . The process of  claim 2 , wherein a weight of ash retained in the upgraded coal product is at least 60 weight percent of ash in the coal. 
     
     
         6 . The process of  claim 1 , wherein a weight of volatile matter retained in the upgraded solid carbonaceous product is from about 10 to about 90 weight percent of volatile matter in the solid carbonaceous material. 
     
     
         7 . The process of  claim 2 , wherein a weight of volatile matter retained in the upgraded coal product is from about 10 to about 90 weight percent of volatile matter in the coal. 
     
     
         8 . The process of  claim 1 , further comprising pretreating the starting solid carbonaceous material prior to heating under partial pyrolysis conditions using at least one of a dryer, a de-asher, and a washer. 
     
     
         9 . The process of  claim 1 , further comprising obtaining an amount of CO 2  greater than about 10 weight % of the volatile matter in the starting solid carbonaceous material. 
     
     
         10 . The process of  claim 1 , further comprising separating the gaseous product from the upgraded solid carbonaceous product. 
     
     
         11 . The process of  claim 11 , further comprising condensing the separated gaseous product into a gaseous stream and a liquid stream. 
     
     
         12 . The process of  claim 11 , further comprising compressing the separated gaseous product resulting in a gaseous stream and a liquid stream. 
     
     
         13 . The process of  claim 1 , further comprising obtaining an amount of a non-condensable fuel gas from about 1 to about 40 weight % of the volatile matter in the starting solid carbonaceous material. 
     
     
         14 . The process of  claim 2 , further comprising obtaining an amount of a non-condensable fuel gas from about 1 to about 40 weight % of the volatile matter in the starting coal. 
     
     
         15 . The process of  claim 1 , further comprising obtaining an amount of LPG greater than from about 1 to about 40 weight % of the volatile matter in the starting solid carbonaceous material. 
     
     
         16 . The process of  claim 2 , further comprising obtaining an amount of LPG greater than from about 1 to about 40 weight % of the volatile matter in the starting coal. 
     
     
         17 . The process of  claim 1 , further comprising obtaining an amount of BTEX from about 0.5 to about 40 weight % of the volatile matter in the starting solid carbonaceous material. 
     
     
         18 . The process of  claim 2 , further comprising obtaining an amount of BTEX from about 0.5 to about 40 weight % of the volatile matter in the starting coal. 
     
     
         19 . The process of  claim 1 , further comprising obtaining an amount of Higher Hydrocarbons from about 0.3 to about 20 weight % of the volatile matter in the starting solid carbonaceous material. 
     
     
         20 . The process of  claim 2 , further comprising obtaining an amount of Higher Hydrocarbons from about 0.3 to about 20 weight % of the volatile matter in the starting coal. 
     
     
         21 . The process of  claim 1 , further comprising obtaining an amount of heteroatom-containing organics that is no greater than 5 weight % of the volatile matter in the starting solid carbonaceous material. 
     
     
         22 . The process of  claim 2 , further comprising obtaining an amount of heteroatom-containing organics that is no greater than 5 weight % of the volatile matter in the starting coal. 
     
     
         23 . The process of  claim 1 , wherein the spent catalyst and the upgraded solid carbonaceous product are recovered as a mixture. 
     
     
         24 . The process of  claim 2 , wherein the spent catalyst and the upgraded solid coal are recovered as a mixture. 
     
     
         25 . The process of  claim 1 , wherein the spent catalyst and the upgraded solid carbonaceous product are recovered separately. 
     
     
         26 . The process of  claim 26 , further comprising regenerating the spent catalyst by contacting the spent catalyst with a mixture of gases containing at least one oxidizing gas to form a regenerated catalyst. 
     
     
         27 . The process of  claim 27 , wherein at least a portion of the regenerated catalyst is heated in the presence of additional solid carbonaceous material in a subsequent partial pyrolysis reaction. 
     
     
         28 . The process of  claim 26 , further comprising regenerating the spent catalyst by acid washing the spent catalyst with an acidic solution to form a regenerated catalyst. 
     
     
         29 . The process of  claim 29 , wherein at least a portion of the regenerated catalyst is heated in the presence of additional solid carbonaceous material in a subsequent partial pyrolysis reaction. 
     
     
         30 . The process of  claim 1 , wherein a weight of total sulfur retained in the upgraded solid carbonaceous product is no more than 80 weight percent of the total sulfur in the starting solid carbonaceous material. 
     
     
         31 . The process of  claim 1 , wherein a weight of organic sulfur retained in the upgraded solid carbonaceous product is no more than 50 weight percent of the organic sulfur in the starting solid carbonaceous material. 
     
     
         32 . The process of  claim 1 , wherein a weight of sulfates retained in the upgraded solid carbonaceous product is no more than 50 weight percent of sulfates in the starting solid carbonaceous material. 
     
     
         33 . A process for converting a solid carbonaceous material in a beneficiation system into a upgraded solid carbonaceous product, the process comprising:
 introducing the solid carbonaceous material and a catalyst into a pyrolysis reactor to produce a gaseous product stream and a solid product stream, wherein the solid product stream comprises the upgraded solid carbonaceous product;   recovering the gaseous product stream from the reactor; and   recovering the solid product stream from the reactor.   
     
     
         34 . The process of  claim 34 , wherein the solid carbonaceous material is coal and the upgraded solid carbonaceous product is an upgraded coal product. 
     
     
         35 . The process of  claim 34 , wherein the catalyst is immobilized in the pyrolysis reactor; and the process further comprises separating the upgraded solid carbonaceous product from the catalyst inside the pyrolysis reactor. 
     
     
         36 . The process of  claim 36 , further comprising:
 recovering a separated spent catalyst from the pyrolysis reactor;   transferring the spent catalyst to a regenerator; and   regenerating the spent catalyst in the regenerator, in which unpyrolyzed coal,   coke, and carbonaceous material are removed from the spent catalyst.   
     
     
         37 . The process of  claim 36 , further comprising:
 transferring the gaseous product stream to a separator; and   at least partially condensing the gaseous product stream in the separator producing a refined gas stream, a hydrocarbon liquid stream, and an aqueous liquid phase stream.   
     
     
         38 . The process of  claim 34 , wherein the solid product stream further comprises a spent catalyst, the process further comprising:
 separating the solid product stream into the upgraded solid carbonaceous product and the spent catalyst after recovering the solid product stream from the pyrolysis reactor, wherein the separated spent catalyst comprises the catalyst and at least one of unpyrolyzed coal, coke, and carbonaceous material.   
     
     
         39 . The process of  claim 39 , further comprising:
 transferring the separated catalyst to a regenerator in which at least a portion of the at least one of the unpyrolyzed coal, coke, and carbonaceous material is removed from the catalyst; and   transferring the gaseous product stream to a separator in which the gaseous product stream is at least partially condensed in the separator producing a refined gas stream, a hydrocarbon liquid stream, and an aqueous liquid phase stream.   
     
     
         40 . The process of  claim 40 , wherein at least a portion of the at least one of the unpyrolyzed coal, coke, and carbonaceous material is removed from the catalyst by at least one of combustion, steam, and a reducing gas. 
     
     
         41 . The process of  claim 39 , wherein the pyrolysis reactor is configured as one of a HERB, a fluidized bed, a moving bed, or an entrained flow bed, and wherein the coal and the catalyst move through the pyrolysis reactor. 
     
     
         42 . The process of  claim 39 , wherein the solid product stream is transferred outside the pyrolysis reactor to a solid-solid separator that separates the upgraded solid carbonaceous product and the spent catalyst. 
     
     
         43 . The process of  claim 39 , wherein the solid-solid separator includes a classifier that separates the upgraded solid carbonaceous product from the spent catalyst based on one of particle size, mass, or density. 
     
     
         44 . The process of  claim 44 , wherein at least one of a size and a density of the spent catalyst is different than at least one of a size and a density of the upgraded solid carbonaceous product, and wherein the classifier of the solid-solid separator separates the upgraded solid carbonaceous product and the spent catalyst based on at least one of size and density. 
     
     
         45 . The process of  claim 34 , further comprising:
 reducing a size of the particles of the solid carbonaceous material in a pulverizer prior to being introduced into the pyrolysis reactor; and   pretreating the solid carbonaceous material in a pretreating device that includes at least one of a dryer configured to dry the coal from the pulverizer utilizing a stream of heated fluid, a washer configured to wash the coal from the pulverizer, and a de-asher configured to remove ash from the coal, wherein the pretreating device is provided between the pulverizer and the pyrolysis reactor.   
     
     
         46 . The process of  claim 46 , wherein the stream of heated fluid is hot flue gas produced by a regenerator during removal of at least a portion of any unpyrolyzed coal, coke, and carbonaceous material from the spent catalyst utilizing an oxygen-carrying gas. 
     
     
         47 . The process of  claim 40 , wherein the separator further includes an acid gas removal system that separates at least one of a sulfur-carrying compound, a nitrogen-carrying compound, and carbon dioxide from the gaseous product stream. 
     
     
         48 . The process of  claim 34 , wherein the catalyst introduced into the pyrolysis reactor includes a first portion comprising regenerated catalyst received from a regenerator and a second portion comprising new catalyst that has not been regenerated, and wherein the first portion of regenerated catalyst has a higher relative temperature than the new catalyst and the coal, such that the regenerated catalyst is a heating medium to heat the coal introduced into the pyrolysis reactor. 
     
     
         49 . The process of  claim 34 , wherein the catalytic pyrolysis of the solid carbonaceous material takes place at a temperature from about 350° C. to about 850° C. 
     
     
         50 . The process of  claim 50 , wherein the solid carbonaceous material introduced into the pyrolysis reactor has a weighted hour space velocity from about 0.2 to about 25 kg/hr per kg of catalyst. 
     
     
         51 . The process of  claim 50 , wherein the solid carbonaceous material has a residence time during the catalytic process from about 0.1 second to about 1 minute. 
     
     
         52 . The process of  claim 34 , wherein a weight ratio of the catalyst to solid carbonaceous material introduced into the pyrolysis reactor is from about 0 to about 100. 
     
     
         53 . The process of  claim 34 , further comprising:
 providing an acid gas removal system that is configured to capture and isolating CO 2  from at least one of the gaseous product from the pyrolysis reactor and a gas from a regenerator configured to regenerate spent catalyst from the pyrolysis reactor; and   obtaining an amount of CO 2  greater than about 4 weight % of the dry ash free coal.   
     
     
         54 . The process of  claim 34 , further comprising obtaining an amount of CO 2  greater than about 10 weight % of the volatile matter in the starting solid carbonaceous material. 
     
     
         55 . The process of  claim 34 , further comprising obtaining an amount of CO 2  greater than about 4 weight % of the dry ash free coal. 
     
     
         56 . The process of  claim 34 , further comprising:
 regenerating a spent catalyst in a regenerator configured to produce a hot flue gas during regeneration; and   transferring at least a portion of the hot flue gas to the pyrolysis reactor to fluidize the pyrolysis reactor.   
     
     
         57 . The process of  claim 57 , wherein a gaseous fluid comprising at least one of CO, CO 2 , water, hydrogen, and oxygen is introduced into the regenerator to facilitate removal of unpyrolyzed coal, coke, and carbonaceous material from the spent catalyst. 
     
     
         58 . The process of  claim 58 , further comprising collecting the hot flue gas that includes CO 2  for one of carbon sequestration or enhanced oil recovery. 
     
     
         59 . The process of  claim 58 , further comprising passing the hot flue gas through a heat exchanger to produce heat that is used to heat the solid carbonaceous material in the pyrolysis reactor. 
     
     
         60 . The process of  claim 57 , wherein the regenerator uses steam in addition to, or instead of, air to remove the coal, coke, and carbonaceous material from the spent catalyst by at least one of hydrolysis and steam gasification. 
     
     
         61 . The process of  claim 57 , wherein the regenerator uses hydrogen or at least one other hydrogen-containing chemical, including hydrocarbons, to reductively remove the coal, coke, and carbonaceous material from the spent catalyst. 
     
     
         62 . The process of  claim 34 , wherein a gas is co-fed into the pyrolysis reactor, wherein the gas comprises at least one light hydrocarbon compound that is recovered from the gaseous product stream. 
     
     
         63 . The process of  claim 63 , wherein the at least one light hydrocarbon compound is recycled back to the pyrolysis reactor. 
     
     
         64 . The process of  claim 63 , further comprising obtaining an amount of BTEX from about 0.5 to about 80 weight % of the volatile matter in the starting solid carbonaceous material. 
     
     
         65 . The process of  claim 34 , wherein a biomass is co-fed into the pyrolysis reactor. 
     
     
         66 . The process of  claim 34 , wherein at least one of an oil shale, a coal derived liquid, a tar sand, and a petroleum is co-fed into the pyrolysis reactor. 
     
     
         67 . The process of  claim 34 , wherein at least one of a wet gas and a natural gas is co-fed into the pyrolysis reactor. 
     
     
         68 . The process of  claim 34 , wherein the pyrolysis reactor includes a stationary catalyst, such that the solid carbonaceous material moves relative to the catalyst through the reactor, to produce the gaseous product stream and the solid product stream, the process further comprising:
 transferring the gaseous product stream to a separator to at least partially condense at least a portion of the gas product stream into a liquid product and a gaseous product; and   wherein the solid product stream contains less than 1 weight part catalyst per 100 parts upgraded carbonaceous product.   
     
     
         69 . A process for converting a biomass in a beneficiation system into an upgraded solid product, the process comprising:
 introducing the biomass and a catalyst into a pyrolysis reactor to produce a gaseous product stream and an upgraded solid product stream, the solid product stream comprising spent catalyst and the upgraded solid product;   separating the upgraded solid product and the spent catalyst;   transferring the separated spent catalyst to a regenerator that removes at least a portion of any unpyrolyzed coal, coke, and other carbonaceous material from the spent catalyst; and   transferring the gaseous product stream to a separator that produces a liquid product and a gaseous product;   wherein a weight of ash retained in the upgraded solid product is at least 60 weight percent of ash in the biomass introduced into the pyrolysis reactor   
     
     
         70 . The process of  claim 1 , wherein an amount of phenol produced is less than an amount of toluene produced on a weight basis. 
     
     
         71 . The process of  claim 1 , wherein an amount of tars produced is less than an amount of light oils produced on a weight basis.