EP2912146A1 - Procédé continu de conversion de lignine en composés utiles - Google Patents

Procédé continu de conversion de lignine en composés utiles

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Publication number
EP2912146A1
EP2912146A1 EP13759462.8A EP13759462A EP2912146A1 EP 2912146 A1 EP2912146 A1 EP 2912146A1 EP 13759462 A EP13759462 A EP 13759462A EP 2912146 A1 EP2912146 A1 EP 2912146A1
Authority
EP
European Patent Office
Prior art keywords
lignin
reactor
slurry
catalyst
conversion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13759462.8A
Other languages
German (de)
English (en)
Inventor
Krishna SHARMA
Aaron MURRAY
Steven RYBA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Biochemtex SpA
Original Assignee
Biochemtex SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/EP2013/053631 external-priority patent/WO2013124461A2/fr
Priority claimed from US13/775,230 external-priority patent/US9139501B2/en
Priority claimed from US13/775,242 external-priority patent/US9340476B2/en
Application filed by Biochemtex SpA filed Critical Biochemtex SpA
Priority to EP13759462.8A priority Critical patent/EP2912146A1/fr
Priority claimed from PCT/EP2013/067734 external-priority patent/WO2014063852A1/fr
Publication of EP2912146A1 publication Critical patent/EP2912146A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
    • C07C37/52—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes
    • C07C37/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by splitting polyaromatic compounds, e.g. polyphenolalkanes by hydrolysis of lignin or sulfite waste liquor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C10G3/52—Hydrogen in a special composition or from a special source
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • PCT/EP2013/053630 filed 26 February 2013, WIPO Application No. PCT/EP2013/053631 filed 26 February 2013, United States Patent Application No. 13/775,229 filed 24 February 2013, United States Patent Application No. 13/775,230 filed 24 February 2013, United States Patent Application No. 13/775,238 filed 24 February 2013, United States Patent Application No. 13/775,239 filed 24 February 2013, United States Patent Application No. 13/775,240 filed 24 February 2013, United States Patent Application No. 13/775,241 filed 24 February 2013, United States Patent Application No. 13/775,242 filed 24 February 2013, United States Provisional Patent Application No. 61/837,262 filed 20 June 2013 and United States Provisional Patent Application No. 61/866,734 filed 16 August 2013 the teachings of each of which are incorporated herein by reference.
  • Boocock, D.G.B et al "The Production of Synthetic Organic Liquids from Wood Using a Modified Nickel Catalyst” discloses exposing air dried poplar to hydrogen and Raney Nickel in a batch autoclave at 340°C to 350°C for 1 or 2 h to produce "oil products".
  • Boocock et al "[t]he use of Raney nickel has now been abandoned in favour of nickel from nickel salts . . .”
  • WO 2011/117705 relies upon dissolving the lignin so that the material can be charged as a liquid taking full advantage of the check valve and high pressure liquid charging systems.
  • WO 2011/117705 "the only limit [is] that the lignin fed to the hydrogenolysis reaction is well dissolved, at the feeding temperature, in said solvent.” Converting the products of a converted lignin feedstream into basic aromatics has been a long desire of industry. There have been attempts to convert the products of a converted lignin feedstream under low-severity conditions ( ⁇ 190° C). However, these conditions have proven unfruitful in yielding selectivity of aromatics in all but a few model compounds.
  • Disclosed herein is a process to convert a converted lignin feedstream to a converted lignin product comprised of aromatic compounds.
  • the process disclosed herein comprises the steps of exposing the converted lignin feedstream to at least one catalyst in the presence of a plurality of hydrogen donor molecules at a reaction temperature in the range of 190 °C to 350° C for a reaction time of at least 30 minutes where the converted lignin feedstream comprises phenol oil, and at least some of the plurality of hydrogen donor molecules are donated during the exposure of the converted lignin feedstream and the plurality of hydrogen donor molecules to the at least one catalyst at the reaction temperature during the reaction time.
  • the at least one catalyst comprises an elemental metal.
  • the first catalyst comprises an elemental metal selected from the group consisting of Platinum, Palladium, Cesium, Copper, Nickel, Ruthenium, Rhodium, Gold, Iron, Cobalt and Iridium.
  • the first catalyst is a bimetallic catalyst comprised of at least one metal selected from the group consisting of Platinum, Palladium, Cesium, Copper, Nickel, Ruthenium, Rhodium, Gold, Iron, Cobalt and Iridium.
  • the ratio of mmol of hydrogen donor molecules to mmol of catalyst is in a range selected from the group consisting of between 1.0: 1.0 and 5.0: 1.0, between 1.2:1.0 and 4.0:1.0 and between 1.5: 1.0 and 3.0: 1.0.
  • At least one of the plurality of hydrogen donor molecules is selected from the group consisting of aliphatic polyols, compounds having the formula of
  • Ri is selected from the group consisting of -OCH 2 , or -H, or -OH and R 2 is selected from the group consisting of -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , and
  • R is selected from the group consisting of -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , and -CH 2 - CH 2 -CH 2 -CH 3 .
  • At least one of the plurality of hydrogen donor molecules is produced from a previously converted lignin feedstream. In one embodiment at least one of the plurality of hydrogen donor molecules is cyclohexanol supplied from a mixture of the converted lignin feedstream and a source other than the converted lignin feedstream. In one embodiment at least one of the plurality of hydrogen donor molecules is selected from the group consisting of sorbitol, glycerol, xylitol and ethylene glycol.
  • the mole ratio of hydrogen donor molecules to phenol oil based upon the phenol oil having an assigned molecular weight of 150.0 g/mol is in a range selected from the group consisting of between 2.0:1.0 and 10.0: 1.0, between 3.0: 1.0 and 9.0:1.0, between 4.0:1.0 and 8.0:1.0 and between 5.0:1.0 and 7.0: 1.0.
  • the reaction temperature is in a range having a lower limit selected from the group consisting of at least 190° C, at least 200° C, at least 210° C, and 215° C and an upper limit selected from the group consisting of 250° C, 260° C, 270° C, 310° C, and 320° C.
  • the process further comprises exposing the converted lignin feedstream to H 2 gas.
  • the amount of H 2 gas is less than 25% of the total amount of hydrogen atoms donated from the at least one hydrogen donating compound and the amount of H 2 gas.
  • Fig. 1 is a schematic description of the unit operations of a fully integrated process for continuously converting ligno-cellulosic biomass feedstock to polyester bottles.
  • Fig. 2 shows a further embodiment of the process.
  • Fig. 3 shows an embodiment with at least a portion of the water from the lignin conversion process reused in the pre-treatment or slurry creation step of an integrated facility.
  • Fig. 4 shows an embodiment of a continuous stir tank reactor for the lignin conversion process.
  • Fig. 5 shows the effect of mixing type and vacuum upon the final dispersed concentration versus time.
  • Fig. 6 shows the schematic of piston pumps and valves used for charging a slurry comprised of lignin to a lignin conversion reactor.
  • Fig. 7 shows the schematic of piston pumps and valves used for charging a slurry comprised of lignin to a lignin conversion reactor.
  • Fig. 8 shows the schematic of a bubble column.
  • Fig. 9 shows the ability of a bubble column to convert the slurry comprised of lignin to lignin conversion products comparable to those attained from a continuous stir tank reactor.
  • This specification is an enabling disclosure and an actual reduction to practice of a continuous lignin conversion process of high yields, in particular from biomass feedstock. Approximately 80% of the available lignin in the feedstock is recovered as usable products.
  • the disclosed process is a very high yield conversion process.
  • 1 kg of biomass feedstock used contained 50% lignin, 41% carbohydrates and 9% ash, by weight of the dry feed.
  • the continuous process produced very little long chain aliphatic hydrocarbons, whereas the comparative batch process produced a significant amount of long chain aliphatic hydrocarbons. It is believed that the continuous process destroyed the carbohydrates to very low molecular weight, low boiling point molecules such as methane and carbon dioxide and removed them through the exit gas. In a batch process, these compounds are kept in the reactor and are believed to be further converted to long chain aliphatics (greater than 12 carbons).
  • the amount of aliphatic carbons having a number of carbons greater than 11 expressed as a percent of the total weight of the conversion products is less than 10% by weight, with less than 8% by weight more preferred, with less than 5% by weight even more preferred with less than 2.5% by weight most preferred.
  • the claimed process utilizes a feed or feedstock comprising lignin. It can also utilize a feedstock consisting of lignin, or a feedstock consisting essentially of lignin, or a feedstock comprising at least 95% lignin by weight.
  • Lignin does not have a single chemical structure.
  • the exact chemical structure of lignin, as it occurs in wood is not known and because it is hard to extract from wood without changing its structure, the exact structure may never be known.
  • the term lignin refers to any polymer comprising p-hydroxyphenyl units, syringyl units, and guaiacyl units.
  • the lignin to be converted in this invention can be present as a feed or feedstock of natural ligno-cellulosic biomass comprising at least one carbohydrate and lignin.
  • a feed or feedstock of natural ligno-cellulosic biomass comprising at least one carbohydrate and lignin.
  • another embodiment of the feedstock may have the composition and unique decomposition temperatures and surface areas described below.
  • the stream will have relatively young carbon materials.
  • the following, taken from ASTM D 6866 - 04 describes the contemporary carbon, which is that found in bio-based hydrocarbons, as opposed to hydrocarbons derived from oil wells, which was derived from biomass thousands of years ago.
  • "[A] direct indication of the relative contribution of fossil carbon and living biospheric carbon can be as expressed as the fraction (or percentage) of contemporary carbon, symbol f . This is derived from f 3 ⁇ 4 through the use of the observed input function for atmospheric 14 C over recent decades, representing the combined effects of fossil dilution of the 14 C (minor) and nuclear testing enhancement (major).
  • Fossil carbon is carbon that contains essentially no radiocarbon because its age is very much greater than the 5730 year half life of 14 C.
  • the faction of modern carbon (1/0.95) where the unit 1 is defined as the concentration of 14 C contemporaneous with 1950 [A.D.] wood (that is, pre- atmospheric nuclear testing) and 0.95 are used to correct for the post 1950 [A.D.] bomb 14 C injection into the atmosphere.
  • a 100% 14 C indicates an entirely modern carbon source, such as the products derived from this process.
  • the percent 14 C of the product stream from the process will be at least 75%, with 85% more preferred, 95% even preferred and at least 99% even more preferred and at least 100% the most preferred. (The test method notes that the percent 14 C can be slightly greater than 100% for the reasons set forth in the method). These percentages can also be equated to the amount of contemporary carbon as well.
  • the amount of contemporary carbon relative to the total amount of carbon is preferred to be at least 75%, with 85% more preferred, 95% even more preferred and at least 99% even more preferred and at least 100% the most preferred.
  • each carbon containing compound in the reactor, which includes a plurality of carbon containing conversion products will have an amount of contemporary carbon relative to total amount of carbon is preferred to be at least 75%, with 85% more preferred, 95% even preferred and at least 99% even more preferred and at least 100% the most preferred.
  • a natural or naturally occurring ligno-cellulosic biomass can be one feed stock for this process.
  • Ligno-cellulosic materials can be described as follows:
  • lignocellulose Apart from starch, the three major constituents in plant biomass are cellulose, hemicellulose and lignin, which are commonly referred to by the generic term lignocellulose.
  • Polysaccharide-containing biomasses as a generic term include both starch and ligno- cellulosic biomasses. Therefore, some types of feedstocks can be plant biomass, polysaccharide containing biomass, and ligno-cellulosic biomass.
  • Polysaccharide-containing biomasses according to the present invention include any material containing polymeric sugars e.g. in the form of starch as well as refined starch, cellulose and hemicellulose.
  • biomasses derived from agricultural crops selected from the group consisting of starch containing grains, refined starch; corn stover, bagasse, straw e.g. from rice, wheat, rye, oat, barley, rape, sorghum; softwood e.g. Pinus sylvestris, Pinus radiate; hardwood e.g. Salix spp. Eucalyptus spp.; tubers e.g. beet, potato; cereals from e.g.
  • the ligno-cellulosic biomass feedstock used to derive the composition is preferably from the family usually called grasses.
  • grasses The proper name is the family known as Poaceae or Gramineae in the Class Liliopsida (the monocots) of the flowering plants. Plants of this family are usually called grasses, or, to distinguish them from other graminoids, true grasses. Bamboo is also included. There are about 600 genera and some 9,000-10,000 or more species of grasses (Kew Index of World Grass Species).
  • Poaceae includes the staple food grains and cereal crops grown around the world, lawn and forage grasses, and bamboo. Poaceae generally have hollow stems called culms, which are plugged (solid) at intervals called nodes, the points along the culm at which leaves arise. Grass leaves are usually alternate, distichous (in one plane) or rarely spiral, and parallel-veined. Each leaf is differentiated into a lower sheath which hugs the stem for a distance and a blade with margins usually entire. The leaf blades of many grasses are hardened with silica phytoliths, which helps discourage grazing animals. In some grasses (such as sword grass) this makes the edges of the grass blades sharp enough to cut human skin. A membranous appendage or fringe of hairs, called the ligule, lies at the junction between sheath and blade, preventing water or insects from penetrating into the sheath.
  • Grass blades grow at the base of the blade and not from elongated stem tips. This low growth point evolved in response to grazing animals and allows grasses to be grazed or mown regularly without severe damage to the plant.
  • a spikelet consists of two (or sometimes fewer) bracts at the base, called glumes, followed by one or more florets.
  • a floret consists of the flower surrounded by two bracts called the lemma (the external one) and the palea (the internal).
  • the flowers are usually hermaphroditic (maize, monoecious, is an exception) and pollination is almost always anemophilous.
  • the perianth is reduced to two scales, called lodicules, that expand and contract to spread the lemma and palea; these are generally interpreted to be modified sepals.
  • the fruit of Poaceae is a caryopsis in which the seed coat is fused to the fruit wall and thus, not separable from it (as in a maize kernel).
  • the success of the grasses lies in part in their morphology and growth processes, and in part in their physiological diversity. Most of the grasses divide into two physiological groups, using the C3 and C4 photosynthetic pathways for carbon fixation.
  • the C4 grasses have a photosynthetic pathway linked to specialized Kranz leaf anatomy that particularly adapts them to hot climates and an atmosphere low in carbon dioxide.
  • C3 grasses are referred to as "cool season grasses” while C4 plants are considered “warm season grasses”.
  • Grasses may be either annual or perennial. Examples of annual cool season are wheat, rye, annual bluegrass (annual meadowgrass, Poa annua and oat). Examples of perennial cool season are orchard grass (cocksfoot, Dactylis glomerata), fescue (Festuca spp), Kentucky Bluegrass and perennial ryegrass (Lolium perenne). Examples of annual warm season are corn, sudangrass and pearl millet. Examples of Perennial Warm Season are big bluestem, indian grass, bermuda grass and switch grass.
  • anomochlooideae a small lineage of broad-leaved grasses that includes two genera (Anomochloa, Streptochaeta); 2) Pharoideae, a small lineage of grasses that includes three genera, including Pharus and Leptaspis; 3) Puelioideae a small lineage that includes the African genus Puelia; 4) Pooideae which includes wheat, barley, oats, brome-grass (Bronnus) and reed-grasses (Calamagrostis); 5) Bambusoideae which includes bamboo; 6) Ehrhartoideae, which includes rice, and wild rice; 7) Arundinoideae, which includes the giant reed and common reed; 8) Centothecoideae, a small subfamily of 11 genera that is sometimes included in Panicoideae; 9) Chlor
  • cereals Agricultural grasses grown for their edible seeds are called cereals.
  • Three common cereals are rice, wheat and maize (corn). Of all crops, 70% are grasses.
  • Sugarcane is the major source of sugar production.
  • Grasses are used for construction. Scaffolding made from bamboo is able to withstand typhoon force winds that would break steel scaffolding. Larger bamboos and Arundo donax have stout culms that can be used in a manner similar to timber, and grass roots stabilize the sod of sod houses. Arundo is used to make reeds for woodwind instruments, and bamboo is used for innumerable implements.
  • Another naturally occurring ligno-cellulosic biomass feedstock may be woody plants or woods.
  • a woody plant is a plant that uses wood as its structural tissue. These are typically perennial plants whose stems and larger roots are reinforced with wood produced adjacent to the vascular tissues. The main stem, larger branches, and roots of these plants are usually covered by a layer of thickened bark. Woody plants are usually either trees, shrubs, or lianas. Wood is a structural cellular adaptation that allows woody plants to grow from above ground stems year after year, thus making some woody plants the largest and tallest plants.
  • xylem vascular cambium
  • conifers there are some six hundred species of conifers. All species have secondary xylem, which is relatively uniform in structure throughout this group. Many conifers become tall trees: the secondary xylem of such trees is marketed as softwood.
  • angiosperms there are some quarter of a million to four hundred thousand species of angiosperms.
  • secondary xylem has not been found in the monocots (e.g. Poaceae).
  • Many non-monocot angiosperms become trees, and the secondary xylem of these is marketed as hardwood.
  • softwood useful in this process is used to describe wood from trees that belong to gymnosperms.
  • the gymnosperms are plants with naked seeds not enclosed in an ovary. These seed "fruits" are considered more primitive than hardwoods.
  • Softwood trees are usually evergreen, bear cones, and have needles or scale like leaves. They include conifer species e.g. pine, spruces, firs, and cedars. Wood hardness varies among the conifer species.
  • the term hardwood useful for this process is used to describe wood from trees that belong to the angiosperm family.
  • Angiosperms are plants with ovules enclosed for protection in an ovary. When fertilized, these ovules develop into seeds.
  • the hardwood trees are usually broad-leaved; in temperate and boreal latitudes they are mostly deciduous, but in tropics and subtropics mostly evergreen. These leaves can be either simple (single blades) or they can be compound with leaflets attached to a leaf stem. Although variable in shape all hardwood leaves have a distinct network of fine veins.
  • the hardwood plants include e.g. Aspen, Birch, Cherry, Maple, Oak and Teak.
  • a preferred naturally occurring ligno-cellulosic biomass may be selected from the group consisting of the grasses and woods.
  • Another preferred naturally occurring ligno- cellulosic biomass can be selected from the group consisting of the plants belonging to the conifers, angiosperms, Poaceae and families.
  • Another preferred naturally occurring ligno- cellulosic biomass may be that biomass having at least 10% by weight of it dry matter as cellulose, or more preferably at least 5% by weight of its dry matter as cellulose.
  • the carbohydrate(s) comprising the invention is selected from the group of carbohydrates based upon the glucose, xylose, and mannose monomers and mixtures thereof.
  • the feedstock comprising lignin can be naturally occurring ligno-cellulosic biomass that has been ground to small particles, or one which has been further processed.
  • One process for creating the feedstock comprising lignin comprises the following steps.
  • pretreatment of the feedstock is a solution to the challenge of processing an insoluble solid feedstock comprising lignin or polysaccharides in a pressurized environment.
  • sizing, grinding, drying, hot catalytic treatment and combinations thereof are suitable pretreatment of the feedstock to facilitate the continuous transporting of the feedstock. While not presenting any experimental evidence, US 2011/0312051 claims that mild acid hydrolysis of polysaccharides, catalytic hydrogenation of polysaccharides, or enzymatic hydrolysis of polysaccharides are all suitable to create a transportable feedstock.
  • US 2011/0312051 also claims that hot water treatment, steam treatment, thermal treatment, chemical treatment, biological treatment, or catalytic treatment may result in lower molecular weight polysaccharides and depolymerized lignins that are more easily transported as compared to the untreated ones. While this may help transport, there is no disclosure or solution to how to pressurize the solid/liquid slurry resulting from the pretreatment. In fact, as the inventors have learned the conventional wisdom and conventional systems used for pressuring slurries failed when pre-treated ligno-cellulosic biomass feedstock is used.
  • pre-treatment is often used to ensure that the structure of the ligno-cellulosic content is rendered more accessible to the catalysts, such as enzymes, and at the same time the concentrations of harmful inhibitory by-products such as acetic acid, furfural and hydroxymethyl furfural remain substantially low.
  • catalysts such as enzymes
  • concentrations of harmful inhibitory by-products such as acetic acid, furfural and hydroxymethyl furfural remain substantially low.
  • the current pre-treatment strategies imply subjecting the ligno-cellulosic biomass material to temperatures between 110-250°C for 1-60 min e.g.:
  • Multistage dilute acid hydrolysis which removes dissolved material before inhibitory substances are formed
  • a preferred pretreatment of a naturally occurring ligno-cellulosic biomass includes a soaking of the naturally occurring ligno-cellulosic biomass feedstock and a steam explosion of at least a part of the soaked naturally occurring ligno-cellulosic biomass feedstock.
  • the soaking occurs in a substance such as water in either vapor form, steam, or liquid form or liquid and steam together, to produce a product.
  • the product is a soaked biomass containing a first liquid, with the first liquid usually being water in its liquid or vapor form or some mixture.
  • This soaking can be done by any number of techniques that expose a substance to water, which could be steam or liquid or mixture of steam and water, or, more in general, to water at high temperature and high pressure.
  • the temperature should be in one of the following ranges: 145 to 165°C, 120 to 210°C, 140 to 210°C, 150 to 200°C, 155 to 185°C, 160 to 180°C.
  • the time could be lengthy, such as up to but less than 24 hours, or less than 16 hours, or less than 12 hours, or less than 9 hours, or less than 6 hours; the time of exposure is preferably quite short, ranging from 1 minute to 6 hours, from 1 minute to 4 hours, from 1 minute to 3 hours, from 1 minute to 2.5 hours, more preferably 5 minutes to 1.5 hours, 5 minutes to 1 hour, 15 minutes to 1 hour.
  • the soaking step can be batch or continuous, with or without stirring.
  • a low temperature soak prior to the high temperature soak can be used.
  • the temperature of the low temperature soak is in the range of 25 to 90°C.
  • the time could be lengthy, such as up to but less than 24 hours, or less than 16 hours, or less than 12 hours, or less than 9 hours or less than 6 hours; the time of exposure is preferably quite short, ranging from 1 minute to 6 hours, from 1 minute to 4 hours, from 1 minute to 3 hours, from 1 minute to 2.5 hours, more preferably 5 minutes to 1.5 hours, 5 minutes to 1 hour, 15 minutes to 1 hour.
  • Either soaking step could also include the addition of other compounds, e.g. H 2 S04, N3 ⁇ 4, in order to achieve higher performance later on in the process.
  • acid, base or halogens not be used anywhere in the process or pre-treatment.
  • the feedstock is preferably void of added sulfur, halogens, or nitrogen.
  • the amount of sulfur, if present, in the composition is in the range of 0 to 1% by dry weight of the total composition. Additionally, the amount of total halogens, if present, are in the range of 0 to 1 % by dry weight of the total composition.
  • the product comprising the first liquid is then passed to a separation step where the first liquid is separated from the soaked biomass.
  • the liquid will not completely separate so that at least a portion of the liquid is separated, with preferably as much liquid as possible in an economic time frame.
  • the liquid from this separation step is known as the first liquid stream comprising the first liquid.
  • the first liquid will be the liquid used in the soaking, generally water and the soluble species of the feedstock. These water soluble species are glucan, xylan, galactan, arabinan, glucolygomers, xyloolygomers, galactolygomers and arabinolygomers.
  • the solid biomass is called the first solid stream as it contains most, if not all, of the solids.
  • the separation of the liquid can again be done by known techniques and likely some which have yet to be invented.
  • a preferred piece of equipment is a press, as a press will generate a liquid under high pressure.
  • the first solid stream is then steam exploded to create a steam exploded stream, comprising solids and a second liquid.
  • Steam explosion is a well known technique in the biomass field and any of the systems available today and in the future are believed suitable for this step.
  • the severity of the steam explosion is known in the literature as Ro, and is a function of time and temperature and is expressed as
  • T expressed in Celsius
  • t expressed in common units.
  • Log(Ro) is preferably in the ranges of 2.8 to 5.3, 3 to 5.3, 3 to 5.0 and 3 to 4.3.
  • the steam exploded stream may be optionally washed at least with water and there may be other additives used as well. It is conceivable that another liquid may be used in the future, so water is not believed to be absolutely essential. At this point, water is the preferred liquid and if water is used, it is considered the third liquid.
  • the liquid effluent from the optional wash is the third liquid stream. This wash step is not considered essential and is optional.
  • the washed exploded stream is then processed to remove at least a portion of the liquid in the washed exploded material.
  • This separation step is also optional.
  • the term at least a portion is removed is to remind one that while removal of as much liquid as possible is desirable (pressing), it is unlikely that 100% removal is possible. In any event, 100% removal of the water is not desirable since water is needed for the subsequent hydrolysis reaction.
  • the preferred process for this step is again a press, but other known techniques and those not invented yet are believed to be suitable.
  • the products separated from this process are solids in the second solid stream and liquids in the second liquid stream.
  • the steam exploded stream is then subjected to hydrolysis to create a hydrolyzed stream.
  • at least a part of the liquid of the first liquid stream is added to the steam exploded stream.
  • water is optionally added.
  • Hydrolysis of the steam exploded stream is realized by contacting the steam exploded stream with a catalyst.
  • Enzymes and enzyme composition is the preferred catalyst. While laccase, an enzyme known to alter lignin, may be used, the composition is preferably void of at least one enzyme which converts lignin.
  • a preferred hydrolysis of the steam exploded stream comprises the step of:
  • the hydrolyzed stream is comprised of carbohydrate monomers selected from the group consisting of glucose, xylose, and mannose.
  • the hydrolyzed stream is subjected to fermentation to create a fermented stream comprised of the composition and water.
  • the fermentation is performed by means of addition of yeast or yeast composition to the hydrolyzed stream.
  • composition derived from naturally occurring ligno-cellulosic biomass is separated from the water in the fermented stream.
  • the separation of the liquid can be done by known techniques and likely some which have yet to be invented.
  • a preferred piece of equipment is a press.
  • the composition is different from naturally occurring ligno-cellulosic biomass in that it has a large surface area as calculated according to the standard Brunauer, Emmett and Teller (BET) method.
  • the BET surface area of the dry composition is at least 4 m /gm more preferably in the range of 4 to 80 m 2 /gm, with 4 to 50 m 2 /gm being more preferable, 4 to 25 m 2 /gm being even more preferred, and 4 to 15 m 2 /gm being even more preferred and 4 to 12 m 2 /gm being the most preferred.
  • composition is further characterized by the peaks generated during a thermal gravimetric analysis, known as TGA.
  • thermogravimetric analysis the plot of the weight with respect to temperature and the plot of the first derivative of weight with respect to temperature are commonly used.
  • the plot of the first derivative of weight with respect to temperature presents a maximum in the specific range of temperature, defined also as first derivative peak.
  • the value of temperature corresponding to the first derivative peak is considered the decomposition temperature of the material or of that component of the material.
  • the material is a composition of many components, which decompose in different specific temperature ranges, the plot of the first derivative of weight with respect to temperature presents first derivative peaks associated to the decomposition of each component in each specific temperature range.
  • the temperature values corresponding to the first derivative peaks are considered the decomposition temperatures of each component of the material.
  • a maximum is located between two minima.
  • the values of temperature corresponding to the minima are considered as the initial decomposition temperature and the final decomposition temperature of the decomposition temperature range of the component whose decomposition temperature corresponds to the first derivative peak comprised between the two minima.
  • a derivative peak corresponds to decomposition temperature range.
  • the weight loss of the material in the range between the initial decomposition temperature and the final decomposition temperature is associated to the decomposition of that component of the material and to the first derivative peak.
  • the mixture of the naturally occurring ligno-cellulosic biomass used to derive the lignin composition is what should be used for the comparison with the material from which the composition was derived.
  • the composition created has the characteristics that temperature corresponding to the maximum value of the first lignin decomposition peak is less than the temperature corresponding to the maximum value of the first lignin decomposition peak of the naturally occurring ligno-cellulosic biomass. This difference is marked with the maximum value of the first lignin decomposition peak being less than the temperature corresponding to the maximum value of the first lignin decomposition peak of the naturally occurring ligno-cellulosic biomass by a value selected from the group consisting of at least 10 °C, at least 15 °C, at least 20 °C, and at least 25 °C.
  • This reduction in the maximum value of the first lignin decomposition temperature can be compared to the maximum value of the first lignin decomposition temperature after pre- treatment.
  • the absolute mass on a dry basis associated with the first lignin decomposition peak of the claimed lignin composition is greater than the absolute mass on a dry basis of the second lignin decomposition peak. While for Arundo donax, the absolute mass of the first decomposition temperature of the naturally occurring ligno-cellulosic biomass is greater than the absolute mass of the second decomposition temperature of the naturally occurring ligno- cellulosic biomass, this is not true for many ligno-cellulosic biomasses such as corn stover and wheat straw. However, after conversion, the lignin composition derived from these biomasses has a mass on a dry basis associated with the first lignin decomposition temperature that is greater than the mass on a dry basis associated with the second lignin decomposition temperature.
  • the feedstock can be further characterized by comparing the temperature associated with the maximum value of the first lignin decomposition range with the temperature associated with the maximum value of the first lignin decomposition range of the ligno-cellulosic biomass used to derive the feedstock.
  • the feedstock can also be further characterized by the relative amount of carbohydrates, which include glucans and xylans, present on a dry basis.
  • the composition may have the amount of total carbohydrates present in the composition in the range of 10 to 60% of the dry weight of the composition, with 10 to 40% more preferred with 5 to 35% even most preferred. Provided, of course, that the amount of total lignin present in the composition is in the range of 30 to 80% of the dry weight of the composition and the weight percent of the carbohydrates plus the weight percent of the lignin is less than 100% of the dry weight of the feedstock.
  • composition of the feedstock comprising lignin may vary with the starting material from which it is derived
  • the naturally occurring ligno-cellulosic biomass from which the feedstock is derived can be selected from the group consisting of the grasses and food crops.
  • Lignin may be charged to a lignin conversion reactor (500) as a solid slurried in a liquid.
  • the liquid may comprise water.
  • the liquid may comprise a hydrogen donor.
  • the use of hydrogen donors is well known and described in Wang, X, and Rinaldi, R.; "Exploiting H-Transfer reactions with RANEY® Ni for upgrade of phenolic and aromatic biorefinery feeds under unusual, low severity conditions:", Energy Environ. Sci., 2012, 5, 8244
  • a slurry comprised of lignin has several unique characteristics making it difficult to create, maintain and handle, and in many instances a slurry comprised of lignin behaves in the opposite manner of traditional slurries.
  • the solid content of a slurry comprised of lignin should be in the range of about 1 to 70% by weight with 5 to 35% by weight solids content more preferred. Traditionally, slurries are easier to maintain when the solids content is low. Surprisingly, a slurry comprised of lignin is easier to maintain when the solids content is high (greater than 20% by weight solids).
  • the particle size of the slurry comprised of lignin should be such that the number average size is in the range of less than 200 micron with less than 150 micron being preferred and less than 100 micron being most preferred. Particle size reduction is not necessary when the feedstock comprising lignin has been steam exploded. However, particle size reduction is considered necessary if the practitioner is starting with naturally occurring lignin, such as wood chips.
  • lignin conversion is co-sited with the pre-treatment or carbohydrate conversion of the ligno-cellulosic biomass (10), then the lignin may already be present in a slurry form, often called the stillage or stillage lignin, with little or no water soluble sugars, or void of water soluble sugars.
  • the ligno-cellulosic biomass (10) is passed through the pre-treatment or carbohydrate conversion process first, the water soluble sugars are converted to species other than sugars.
  • the water soluble sugars will have been washed off, extracted or converted by the enzymes or catalysts to species other than sugars, leaving the bottoms which are comprised of lignin and unconverted, insoluble carbohydrates, many of which are still bound with the lignin. These bottoms are void of or substantially void of free water soluble sugars.
  • the bottoms, (or stiUage or stiUage lignin as it is often called), of the sugar or carbohydrate conversion process, (e.g. fermentation), are passed directly to a next process which could further remove more carbohydrates; or the bottoms are passed directly to the lignin conversion process described herein.
  • the water from the carbohydrate conversion process which would otherwise have to be treated via expensive waste water treatment plant(s) is used as a slurry liquid to maintain or create the slurry comprised of lignin to feed the lignin conversion process.
  • the stiUage lignin which is the slurry liquid removed from the carbohydrate conversion process comprising the lignin, is then cleaned in situ by the hydrogen of the lignin conversion process while at the same time, converting the lignin.
  • the slurry liquid coming from the lignin conversion process will have significantly less total biochemical oxygen demand, also known as BOD's, and/or chemical oxygen demand, also known as COD's, relative to the amounts of BOD's and COD's in the incoming slurry liquid from the stiUage lignin, thus reducing the amount of, and cost of waste water treatment needed before releasing the slurry liquid to the environment.
  • BOD's and COD's have been chemically destroyed by the conditions of the lignin conversion process.
  • At least a portion of the slurry liquid from the lignin conversion process can be used as make up water or steam in a pre-treatment process, thus significantly reducing the amount and cost of water treatment. (See Fig. 3)
  • ligno-cellulosic biomass (10) enters the pre-treatment process and the pre-treated ligno-cellulosic biomass is passed to the carbohydrate conversion process, in this instance fermentation.
  • carbohydrate conversion process the sugars are converted to the final product or products.
  • the bottoms, or stillage comprising the lignin, slurry liquid, and possibly carbohydrates, is passed to the slurry creation step, (300). If the stillage lignin is a sufficiently stable slurry and of desired concentrations, (e.g. solids, buffers, pH), it can be passed directly to (400), the slurry pump, without any further treatment, e.g. water dilution or water reduction, agitation, vacuum.
  • desired concentrations e.g. solids, buffers, pH
  • the slurry comprised of lignin is brought to the optimum slurry conditions by adjusting the solids concentration under agitation and optionally vacuum. Usually this is under high shear agitation of the slurry comprised of lignin.
  • the bottoms of the carbohydrate conversion process will be shipped to a different location for the lignin conversion. While it is possible to ship the already slurried stillage, the cost of shipping water may make shipping cost prohibitive. In this instance, it is anticipated that the feedstock comprised of lignin will be shipped as a solid and often dry with as much water having been removed as possible; usually by a filter press, drying, or both. Oftentimes, the solid feedstock comprising lignin will be chilled or even frozen to prevent microbial growth during shipment or storage.
  • the slurry liquid from the dewatering process is often sent to waste water treatment where it is cleaned to remove BOD's and COD's, and then released to the environment or reused in parts of the pre-treatment process. It is this external treatment step which can be minimized or reduced by re-using or recycling at least a portion of the slurry liquid from the lignin conversion process.
  • one strategy for creating the slurry comprised of lignin is to use a machine capable of applying high shear forces and apply high shear forces to the unslurried solid feedstock comprising lignin.
  • High shear forces may be achieved by feeding the solid feedstock comprising lignin through a compounder.
  • Preferred compounder embodiments include a twin screw co-rotating screws compounder, a twin screw counter-rotating screws compounder, an extruder, a banbury, or another device known for imparting mechanical forces to the material processed through it.
  • the amount of mechanical forces required is related to the amount of energy required to make the solid feedstock comprising lignin readily dispersible. The more mechanical forces applied to the solid feedstock comprising lignin, the easier the dispersion. The amount of mechanical forces required can be determined iteratively by comparing the energy consumed with the energy required to disperse the resulting solid into the slurry liquid of the slurry. Techniques to vary the amount and type of mechanical forces applied to the solid feedstock comprising lignin depend upon the equipment and are well known in the art to those familiar with the particular machine being used.
  • a slurry liquid can be added to the solid feedstock comprising lignin to produce a slurry comprised of lignin. It is preferred that the slurry liquid be added to the solid feedstock comprising lignin after exiting the compounder. In this regard, the solid feedstock comprising lignin is void of free liquid meaning that free liquid comprises less than 5% of the weight of the composition with no free liquid being preferred.
  • the slurry liquid may be added to the solid feedstock comprising lignin in the compounder.
  • the slurry liquid comprises water.
  • the slurry liquid may comprise a hydrogen donor. It should be noted that for the purposes of this specification, the slurry liquid is also known as a carrier liquid as well.
  • the amount of energy consumed by the compounder necessary to create a solid feedstock comprising lignin that is readily dispersible into a slurry liquid and/or has a low viscosity when dispersed into a slurry liquid can be determined by measuring the torque.
  • the solid feedstock comprising lignin is readily dispersed into a slurry liquid when the amount of torque required to disperse the solid feedstock comprising lignin into the slurry liquid in the absence of a hydrolysis catalyst is less than 50% of the amount of torque required to disperse the solid feedstock comprising lignin into the slurry liquid under the same conditions, prior to the application of the mechanical forces.
  • the amount of torque is the total amount of energy applied to the solid-slurry liquid mixture to disperse the solid into the slurry liquid.
  • the amount of torque can be determined by the area under the curve of the line of the torque applied at a given point in time, t, corresponding to the point at which the solid is considered dispersed into the slurry liquid.
  • a solid is considered dispersed into the slurry liquid when the numeral average of the percent of dry matter content of a statistically valid number of aliquots of the slurry liquid is within 2.5% of the percent of the total dry matter content in the slurry liquid.
  • the viscosity of the slurry comprised of lignin, measured at 25 °C, a shear rate of lOs-1, of the mechanically dispersed solid feedstock comprising lignin dispersed in the slurry liquid content should be less than the viscosity of a slurry of the solid feedstock comprised of lignin dispersed in the slurry liquid prior to mechanical treatment; when measured under the same conditions (e.g. dry matter content).
  • the slurry comprised of lignin may be maintained by way of mechanical agitation.
  • Another strategy for creating the slurry comprised of lignin where the lignin conversion is not co-sited with the pre-treatment or fermentation of the ligno-cellulosic biomass (10) is to expose the solid feedstock comprising lignin in a slurry liquid, preferably water, to a vacuum or pressure less than atmospheric pressure, with less than 0.8 bar being preferred, with less than 0.7 bar being more preferred, less than 0.4 bar being even more preferred with less than 0.2 bar being the most preferred.
  • the feedstock comprising lignin will rapidly expand into small particles, disassociate, and disperse. In this way, high shear mixing and/or high shear forces are avoided with higher concentrations possible.
  • the Slurry Creation Experimental Section and Figure 5 quantitatively show the advantage of using vacuum on the solid feedstock comprising lignin prior to increasing the pressure on the slurry.
  • the vacuum may be applied simultaneously with shear and agitation, through a conveying screw.
  • the minimum time for the vacuum to remain applied is the time sufficient to disperse the particles to greater than 50% of the theoretical dispersion at 25°C, with greater than 75% dispersion at 25°C more preferred and greater than 90% dispersion at 25°C the most preferred.
  • the solid feedstock comprising lignin be surrounded or encompassed by a slurry liquid for full effectiveness of the vacuum.
  • this slurry liquid is water. In another embodiment, this slurry liquid comprises a hydrogen donor. 100% dispersion at 25 °C is the theoretical dispersion. The amount of dispersion is determined by measuring the amount of solids in a sample after 2 minutes of settling. If there were 16 gms of solid in 84 gms of liquid, the dry matter content at 100% dispersion would be 16 %. At 50% of the theoretical dispersion, the dry matter content of the sample after 2 minutes of settling would be 8%.
  • a final strategy for creating the slurry comprised of lignin where the lignin conversion is not co-sited with the pre-treatment or fermentation of the ligno-cellulosic biomass (10) is to expose the solid feedstock comprising lignin in a slurry liquid, preferably water, to high shear such as that found in a blender, which over time will also disperse the particles of the feedstock comprising lignin throughout the slurry.
  • the slurry liquid is a hydrogen donor.
  • the slurry liquid will be water or water in combination with at least one hydrogen donor.
  • the ratio amount of the weight of the water of the slurry liquid to the dry weight of the lignin feedstock is preferably in the range of 0.3 to 9, with 0.5 to 9 more preferred, with 1 to 9 even more preferred with 2 to 9 another preferred ratio and 3 to 5 an even more preferred ratio.
  • the flask had a dimension of approximately 16cm and was equipped with a stirrer with a dimension of approximately 6cm.
  • the flask was sealed and vacuum of 29.8mmHg was applied for 5 minutes and removed. After 2 minutes of sedimentation time, a first sampling of the slurry comprised of lignin was extracted.
  • a control experiment was realized by inserting an amount of 450g of lignin-rich composition, having a dry matter of 53%, into a 3 liter round bottom flask with 1050g of water, to reach a theoretical concentration of 16% of dry matter of lignin-rich composition in the mixture.
  • the flask and mechanical stirrer were the same as in the experiment conducted with vacuum.
  • the slurry comprised of lignin was subjected only to mechanical agitation, and samplings were extracted after 5, 1, 5, 10, 30, 60 minutes of agitation. Before each sampling, the mechanical agitation was stopped for 2 minutes of sedimentation time.
  • the mechanical agitation was obtained by stirring the slurry comprised of lignin at 250rpm in both the experiments.
  • Concentration of dry matter of the lignin-rich composition was determined by drying samples in an oven at 105°C for 15 hours.
  • Figure 5 reports the graph of percent complete dispersion of the lignin-rich composition in the slurry comprised of lignin.
  • the percent complete dispersion is the concentration of dry matter of lignin-rich composition in the slurry comprised of lignin normalized with respect to the theoretical concentration.
  • the experiment demonstrates that by applying a vacuum the time needed to obtain a full dispersion of the lignin-rich composition in the slurry comprised of lignin is strongly reduced, thereby enabling mixing energy savings, time savings and slurry tank volume reduction.
  • the slurry comprised of lignin can be pressurized using a slurry pump (400).
  • a slurry pump (400) is meant to refer to any pump which can reach the desired pressures, such as a piston pump and/or a syringe pump.
  • a multi-stage centrifugal pump may also reach the required pressures.
  • the slurry pump (400), which is depicted as a piston pump used in the experiments will have an inlet valve (350). The inlet valve position can span the range from fully open to fully closed.
  • the inlet valve position can be selected from the group consisting of open, closed and at least partially open, wherein open means fully open (the restrictions across the valve as measured by pressure drop are the minimum possible), closed means fully closed so that no liquid or gas can pass through the valve, and at least partially open means the valve is not fully closed and not fully open, but somewhere in between fully closed and fully open.
  • the slurry pump (400) will have an outlet valve (450).
  • the outlet valve can be present in an outlet valve position selected from the group consisting of open, closed and at least partially open, with open, closed and at least partially open having the same meanings as for the inlet valve position.
  • the slurry pump (400) will further comprise a piston (420) and a piston chamber (425).
  • the piston (420) forms a seal inside and against the piston chamber (425) to form a pump cavity.
  • the size of the cavity depends upon where the piston (420) is within the piston chamber (425).
  • the slurry comprised of lignin is passed through the inlet valve (350) which is in the inlet valve position of at least partially open or open (430A) into the pump cavity formed by withdrawing at least a portion of the piston (420) from the piston chamber (425).
  • the outlet valve (450) is in the closed outlet valve position (440B).
  • the pump cavity will be at an inlet pump cavity pressure.
  • the inlet valve position is changed to closed (430B), or in other words, the inlet valve is closed.
  • a force is then placed on or applied to the piston (420) in the piston chamber (425) until the pressure of the slurry comprised of lignin reaches the discharge pressure which is greater than the reactor operating pressure, also known as the lignin conversion reactor pressure or deoxygenation pressure.
  • the reactor operates in the ranges of 80 to 245 bar, 80 to 210 bar, 90 to 210 bar and 90 to 175 bar. Therefore the discharge pressure of the pump should also be in the above ranges of 80 to 245 bar, 80 to 210 bar, 90 to 210 bar and 90 to 175 bar, but greater than the lignin conversion pressure. It should also be noted for the purposes of this specification that the terms lignin conversion vessel and lignin conversion reactor are interchangeable.
  • At least a portion of the slurry comprised of lignin is discharged from the pump cavity by opening the outlet valve (450), also known as changing the outlet valve position to a position selected from the group consisting of at least partially open and open.
  • the piston (420) is further forced into the pump body to reduce the volume of the pump cavity and push at least a portion of the slurry comprised of lignin through the outlet valve (450).
  • the outlet valve (450) is connected to the lignin conversion reactor (500) by tubing, piping or other connection.
  • connected to the lignin conversion reactor it is meant that material from the pump cavity can flow through the outlet valve and into the lignin conversion reactor (500) generally through a pipe, a tube or through a series of connected pipes or tubes.
  • the slurry comprised of lignin is continuously introduced to the lignin conversion reactor (500).
  • the slurry comprised of lignin is introduced into the lignin conversion reactor (500) in steady aliquots or pulses.
  • the mass introduced into the lignin conversion reactor equals the mass removed from the lignin conversion reactor.
  • One distinguishing feature between a continuous and a batch process is that, in a continuous process, the reaction is occurring or progressing at the same time that either the slurry comprised of lignin is introduced into the lignin conversion reactor (500) and/or the lignin conversion products are removed from the lignin conversion reactor.
  • Another way to state this is that the conversion (e.g. deoxygenating, or hydrogenating) in the lignin conversion reactor occurs while simultaneously, or at the same time, removing at least a portion of the lignin conversion reactor contents from the lignin conversion reactor (500). Such removal is done in a continuous manner which includes an aliquot or pulse removal.
  • unobstructed flow it is meant that the flow path does not contain any additional elements, such as the insert body of a butterfly valve, in the path of the slurry flow such that the slurry will have to flow around or strike the additional element when the valve is in the fully open position.
  • the flow path does not contain additional dead zones, such as the seat groove of a gate valve. Dead zones, such as the seat groove of a gate valve will fill with slurry when the valve is open and, when the valve is closed, the gate will compress the slurry into the groove which will allow for accumulation and compression of the slurry comprised of lignin in the groove. In this instance, over time the valve will not seat or seal, and will fail to hold pressure.
  • a valve that provides for unrestricted and unobstructed flow of the slurry comprising lignin may include a ball valve, a full port ball valve or a full port fixed ball valve.
  • traditional valves such as most globe valves, most angle valves, most diaphragm valves, most butterfly valves and most check valves restrict and/or obstruct the flow of the slurry comprised of lignin and will cause the lignin from the slurry comprised of lignin to build up in areas of low flow or high impaction causing the valves to eventually plug or not seat or seal, and fail to hold pressure.
  • the process only functioned when the inlet valve (350) and the outlet valve (450) were not check valves, but valves that provide for unrestricted and unobstructed flow.
  • a check valve being a valve which prevents the reversal of flow. It is preferable that the pressurization process, discharge and ultimate charge into the reactor be void of any check valves in the path of slurry flow. Alternatively, the slurry does not flow through a check valve into the slurry pump (400) to enter the reactor.
  • each piston pump may have its own inlet valve and its own outlet valve (e.g. the first piston pump has a first inlet valve (350A) and a first outlet valve (450A) while the second piston pump has a second inlet valve (350B) and a second outlet valve (450B)).
  • the plurality of slurry pumps can be in a parallel configuration. It is possible for two piston pumps in a parallel configuration to share the same inlet valve (350) and/or outlet valve (450). Another configuration is where the inlet valve (350) and outlet valve (450) are the same valve.
  • the lignin conversion reactor will have a lignin conversion pressure and lignin conversion temperature.
  • the lignin conversion pressure will be at least slightly less than the slurry pump discharge pressure which is at least the amount of pressure drop from the slurry pump (400) to the lignin conversion reactor inlet.
  • the slurry pump discharge pressure will be greater than the lignin conversion pressure, with the slurry pump discharge pressure being greater than the lignin conversion reactor pressure plus the absolute amount of pressure drop in the process from the slurry pump discharge to the lignin conversion reactor (500).
  • De-ionized water was added to a lignin-rich composition obtained from the pretreatement of ligno-cellulosic biomass to obtain a slurry comprised of lignin having a dry matter content of 20 weight percent of the mass of the slurry.
  • the mixture was inserted into a blender (Waring Blender, model HGBSSSS6) and thoroughly mixed intermittently for one to two minutes to reach a homogeneous slurry. The homogeneity of the slurry was evaluated by eye.
  • the slurry was inserted into a mix tank (340) with constant agitation.
  • the mix tank (340) was a stainless steel, dish bottom tank with a volume of approximately 1 L containing a standard laboratory paddle mixer and a bottom discharge port connected to a Chandler Quizix QX dual syringe pump having two pump cavities.
  • Inlet valves (350) were inserted between the mix tank (340) and the two pump cavities of the Chandler Quizix QX dual syringe pump.
  • the Chandler Quizix QX dual syringe pump was connected by tubing to a Parr 4575 reactor equipped with a dual 45° pitched turbine blade, cooling coil, separate gas and slurry feed ports and a discharge dip tube (610).
  • Outlet valves (450) were inserted between the two pump cavities of the Chandler Quizix QX dual syringe pump and the Parr reactor.
  • the slurry comprised of lignin was passed from the mix tank (340) into the first of the two pump cavities of the Chandler Quizix QX dual syringe pump by changing the inlet valve position of the first inlet valve (350A) corresponding to the first pump cavity to the open position (430A) by means of an actuator. After the slurry comprised of lignin reached the first pump cavity, the first inlet valve (350A) corresponding to the first pump cavity was changed to the closed inlet valve position (430B) by means of an actuator.
  • the slurry comprised of lignin was passed from the mix tank (340) into the second of the two pump cavities of the Chandler Quizix QX dual syringe pump by changing the inlet valve position of the second inlet valve (350B) corresponding to the second pump cavity to the open position (430A) by means of an actuator.
  • the Chandler Quizix QX dual syringe pump pressurized the slurry comprised of lignin in the first pump cavity to a pressure greater than that of the Parr reactor. While the slurry comprised of lignin in the first pump cavity was being pressurized both the first inlet valve (350A) and the first outlet valve (450A) were closed.
  • the first outlet valve (45 OA) corresponding to the first pump cavity was changed to the open position (440A) by means of an actuator, allowing the pressurized slurry comprised of lignin in the first pump cavity to be charged to the Parr reactor.
  • the second inlet valve (350B) corresponding to the second pump cavity was changed to the closed position (430B) by means of an actuator.
  • the Chandler Quizix QX dual syringe pump pressurized the slurry comprised of lignin in the second pump cavity to a pressure greater than that of the Parr reactor. While the slurry comprised of lignin in the second pump cavity was being pressurized both the second inlet valve (350B) and the second outlet valve (450B) were closed.
  • the pressure of the Parr reactor is the deoxygenation pressure and can range from 90 to 175 bar.
  • the first outlet valve (450A) corresponding to the first pump cavity was changed to the closed position (440B) by means of an actuator.
  • the second outlet valve (450B) corresponding to the second pump cavity was changed to the open (440A) position by means of an actuator, allowing the pressurized slurry comprised of lignin in the second pump cavity to be charged to the Parr reactor.
  • the first inlet valve (350A) corresponding to the first pump cavity was changed to the open position (430A) by means of an actuator, allowing additional slurry comprised of lignin from the mix tank (340) into the first pump cavity to be pressurized and subsequently charged to the Parr reactor.
  • inlet valves and outlet valves were small orifice, rising stem valves from Vindum Engineering, Model No. CV-505-SS. These valves were recommended by an expert in the field of slurry pumping, and were represented as sufficient for charging a slurry comprised of lignin to a pressurized reactor.
  • the inlet valve corresponding to the first pump cavity was changed to the open position, it allowed a portion of the slurry comprised of lignin into the first pump cavity to be charged to the Parr 4575 reactor.
  • the inventors decided to replace the inlet valves with Swagelok 60 Series 3 piece Ball Valves, Model No. SS-62TS6.
  • the outlet valves were the same Swagelock Bellows Seal Valves used in Experiments 3 and 4.
  • the inlet valve corresponding to the first pump cavity was changed to the open position, it allowed a portion of the slurry comprised of lignin into the first pump cavity, which was subsequently passed through the outlet valve corresponding to the first pump cavity and charged to the Parr reactor.
  • the process was run for a period of approximately two days, at which time the outlet valves became plugged with solid lignin from the slurry comprised of lignin.
  • the inlet valves were the same Swagelok 60 Series 3 piece Ball Valves as those used in Experiment 5, however, the inventors decided to replace the outlet valves with Swagelok 60 Series 3 piece Ball Valves, Model No. SS-62TS6.
  • the inlet valve corresponding to the first pump cavity was changed to the open position, it allowed a portion of the slurry comprised of lignin into the first pump cavity, which was subsequently passed through the outlet valve corresponding to the first pump cavity and charged to the Parr reactor.
  • the pump was then able to continuously charge the slurry comprised of lignin into the Parr reactor without plugging the inlet valves or outlet valves. It was not necessary to pressurize the mix tank (340) in order to charge the reactor.
  • the deoxygenation which is the exposure of the lignin to hydrogen as either H 2 gas or via a hydrogen donor, occurs at a lignin conversion temperature and a lignin conversion pressure, wherein the lignin conversion temperature is in the range of greater than the boiling point of the liquid composition in the reactor at atmospheric pressure, and less than the critical temperature of the liquid composition, with the lignin conversion pressure being greater than the bubble pressure of the liquid composition in the reactor at the lignin conversion temperature, subject to the condition that the lignin conversion pressure is selected so as to avoid the formation of char.
  • the liquid composition of the reactor is the composition of the liquid components that are added to the vessel.
  • the liquid composition is almost pure water with dissolved species.
  • the hydrogen would come from added hydrogen gas.
  • the bubble pressure is the vapor pressure of the water at the lignin conversion temperature.
  • the liquid composition could comprise water and a hydrogen donor. This liquid composition has its own bubble pressure and critical temperature forming the lower and upper boundary of the temperature range, subject to the additional condition that the lignin conversion pressure be selected so as to avoid char formation after two residence cycles, which can be visually verified by opening the reactor after two residence cycles and observing the presence or absence of char - a dark residue coating the reactor.
  • the reactor will also be void of any liquid. What has been discovered is that the lignin conversion pressure is also a function of the amount of gas exiting the reactor. The higher the amount of gas used, such as in hydrogen gas or nitrogen, the greater the pressure required. In the instance of a hydrogen donor, less gas is used and thus a lower lignin conversion pressure is needed to prevent char.
  • gas such as in hydrogen gas or nitrogen
  • the proper lower lignin conversion pressure can be easily empirically established as follows.
  • a residence cycle is the amount of time to turn over the reactor contents. If the residence volume is 4 L in the vessel and the vessel is being charged at a volumetric flow rate at operating conditions of 1 L/hr, the residence cycle is 4 hours and 2 residence cycles is 8 hours. At 2 L/hr, the residence cycle is 2 hrs and 2 residence cycles is 4 hours.
  • the lignin conversion process should occur at a lignin conversion temperature, where the lignin conversion temperature is in the range of greater than the boiling point of the slurry liquid at atmospheric pressure, and less than the critical temperature of the slurry liquid, subject to the condition that the lignin conversion pressure is greater than the bubble pressure of the slurry liquid at the lignin conversion temperature and the lignin conversion pressure is selected so as to avoid the formation of char.
  • the lignin conversion pressure should be selected so that the lignin conversion pressure is greater than the bubble pressure of the slurry liquid at the lignin conversion temperature.
  • Bubble pressure is the sum of the partial vapor pressures of all components in the lignin conversion reactor.
  • the lignin conversion process should occur at a lignin conversion temperature below the critical temperature of water.
  • the lignin conversion process will occur at a lignin conversion temperature in the range of 190°C to 370°C.
  • the lignin conversion temperature range is preferably selected from the group consisting of 190°C to 370°C, 210°C to 370°C, 220°C to 360°C, 240°C to 360°C, 250°C to 360°C, 280°C to 360°C, 290°C to 350°C, and 300°C to 330°C.
  • the lignin conversion process may occur at a lignin conversion temperature in the range of 190°C to 350°C with 200°C to 310°C being more preferred, 210°C to 300°C being even more preferred, and 210°C to 280°C being most preferred.
  • the hydrogen donor may also be introduced into the lignin conversion reactor separately from the liquid slurry.
  • the hydrogen donor may also come from the carbohydrate conversion step, thus the ligno-cellulosic biomass is generating its own hydrogen for use in the process.
  • the hydrogen donor such as ethylene glycol, could be manufactured in the carbohydrate conversion step of Figure 3 and passed to the liquid slurry and introduced into the lignin conversion reactor via stream 325.
  • the lignin conversion pressure is in a range preferably selected from the group consisting of 70 bar to 300 bar, 80 bar to 245 bar, 82 bar to 242 bar, 82 bar to 210 bar, 90 bar to 207 bar and 90 bar to 172 bar.
  • the continuous lignin conversion in the presence of carbohydrates should occur at a lignin conversion pressure higher than the theoretical equilibrium vapor pressure of water at the lignin conversion temperature. It was directly observed that char was formed when the lignin conversion pressure was even greater than the calculated water vapor pressure at the lignin conversion temperature accounting for the exiting gas sweeping across the top of the liquid.
  • De-ionized water was added to a lignin-rich composition obtained from the pretreatement of ligno-cellulosic biomass to obtain a slurry comprised of lignin having a dry matter content of 20 weight percent of the mass of the slurry.
  • the mixture was inserted into a blender (Waring Blender, model HGBSSSS6) and thoroughly mixed intermittently for 10 min. to reach a homogenous slurry. The homogeneity of the slurry was evaluated by eye.
  • the slurry was inserted into a mix tank with constant agitation.
  • the mix tank was a stainless steel, dish bottom tank with a bottom discharge port connected to a Chandler Quizix QX dual syringe pump having two pump cavities.
  • Inlet valves were inserted between the mix tank and the two pump cavities of the Chandler Quizix QX dual syringe pump.
  • the Chandler Quizix QX dual syringe pump was connected by tubing to a Parr 4575 reactor equipped with a dual 45° pitched turbine blade, cooling coil, separate gas and slurry feed ports and a discharge dip tube.
  • Outlet valves were inserted between the two pump cavities of the Chandler Quizix QX dual syringe pump and the Parr reactor.
  • Hydrogen at a temperature of 20° C was inserted into the Parr reactor to reach a pressure of 48.3 bar.
  • the Parr reactor was heated to a temperature corresponding to 90% of the reaction temperature and continuous flow of Hydrogen was started into the Parr reactor.
  • the pressure was measured by means of a pressure transducer (Ashcroft Type 62) connected to the Parr reactor.
  • the slurry comprised of lignin was passed from the mix tank through the Chandler Quizix QX dual syringe pump and into the Parr reactor by opening and closing the inlet and outlet valves in a manner that allowed the slurry comprised of lignin to pass continuously into the Parr reactor.
  • liquid present such as water in the liquid phase
  • the lignin conversion catalyst is present as free particles (625), and not a fixed bed, the lignin conversion catalyst needs separated from the lignin conversion products.
  • the catalyst particles (625) can be separated from the liquid lignin conversion products after the liquid lignin conversion products are removed from the lignin conversion reactor (500) by filtering, settling, centrifuging, solid bowl centrifuging, cycloning or other processes known in the art.
  • the separated catalyst is then either re-introduced into the lignin conversion reactor for further reactions, treated for replenishment and then reused, or discarded. These traditional methods are known.
  • the free catalyst particles (625) can be separated from the lignin conversion products in situ, that is within the lignin conversion reactor (500) while the continuous catalytic conversion of the lignin feedstock to lignin conversion products is occurring.
  • the lignin conversion products can be separated from the catalyst particles (625) during the continuous catalytic conversion of a lignin feedstock to lignin conversion products. This separation is done by gravity settling, wherein the fluid linear velocity (meters/min) of the lignin conversion products (liquid and gas) leaving the lignin conversion reactor is less than the gravitational linear settling velocity of the catalyst particles (625) in the liquid/gas lignin conversion product stream exiting the reactor.
  • the liquid level of the lignin conversion reactor is at the physical interface of the bulk liquid phase and bulk gas phase in the lignin conversion reactor (500).
  • the bulk gas phase is a continuous gas phase which has a specific gravity which is less than the specific gravity of the bulk liquid phase.
  • the bulk gas phase may have droplets of liquid in the bulk gas phase.
  • the bulk liquid phase is a continuous liquid phase and will have dissolved gases and gas bubbles.
  • the disengagement height is greater than the catalysts particles travel height which is the height the catalyst particles (625) will reach when carried along with the lignin conversion products. Because the settling velocity of the catalyst particles is greater than the lignin conversion products removal velocity, the catalyst particles (625) will eventually drop back into the lignin conversion reactor (500) so long as the disengagement height in the settling zone as discussed below is large enough relative to the travel height so that at least a majority of the catalyst particles (625) do not reach the point at which the lignin conversion products are removed from the lignin conversion reactor.
  • the disengagement height should be large enough so that at least a majority of the catalyst particles (625) never reach the point at which the liquid lignin conversion products are removed from the lignin conversion reactor.
  • the disengagement point must be less than the dip tube minor length (614).
  • the dip tube minor length (614) is one meter
  • the settling velocity of the catalyst particles is 1.2 meters per second
  • the liquid lignin conversion products removal velocity is 1 meter per second
  • the liquid lignin conversion products will reach the disengagement height (which is also the dip tube minor length (614)) in one second.
  • the catalyst particles (625) have a settling velocity which is 0.2 meters per second greater than the liquid lignin conversion products velocity
  • the catalyst particles (625) will travel up the dip tube (610) at a velocity which is 0.2 meters per second less (0.8 meters per second in this example) than the liquid lignin conversion products travel up the dip tube.
  • the catalyst particles (625) will reach or exceed the disengagement height and will be removed from the reactor. For instance, if the settling velocity of the catalyst particles is 0.8 meters per second and the liquid lignin conversion products removal velocity is 1 meter per second, the catalyst particles (625) will be travelling at a velocity at least equal to the liquid lignin conversion products. In this manner the catalyst particles will reach the disengagement height at least at the same time as the liquid lignin conversion products, and will thereby be removed from the lignin conversion reactor (500) through the dip tube (610).
  • the lignin conversion reactor will have an agitation zone and a settling zone, also known as a decantation zone.
  • the liquid phase of the reactor is exposed to less agitation than in the agitation zone.
  • the settling zone can be created by use of a dip tube as discussed below. The internal of the dip tube sees very little agitation and is thus the settling zone in that embodiment.
  • the settling zone can also be created by placing baffles above the agitator but below the liquid level to create a still spot. Another way is to have a separate reactor or vessel which does not have agitation. This configuration is described in the bubble column section.
  • the lignin conversion products are removed from the settling zone at a lignin conversion products removal velocity.
  • the lignin conversion products removal is subject to the condition that to reach the point in the lignin conversion reactor which is higher relative to gravity than the liquid level of the lignin conversion reactor, the lignin conversion products must leave the agitation zone and pass through a portion of the settling zone
  • Figure 4 demonstrates an embodiment of the principles.
  • the product is removed via a dip tube (610), where the lignin conversion products must exit up and out the dip tube.
  • the first catalyst particles (625) travel with it.
  • the first catalyst particle will have a terminal or settling velocity - that is the speed at which the particle drops through the liquid lignin conversion products of the reactor.
  • catalyst particles (625) coming out the dip tube (610) it is a simple matter to enlarge the diameter of the dip tube to reduce the lignin conversion products velocity relative to gravity (slow down the speed) so that the conversion products travel up the tube relative to gravity at a speed less than the speed at which the first catalyst particles are dropping down the tube, thus keeping the catalyst in the reactor. If one wished to purge the catalyst, or add new catalyst so that the old catalyst could be removed, one would reduce the diameter of the tube (increasing the flow rate) and have catalyst particles (625) flow out of the lignin conversion reactor (500). The catalyst removal and replenishment can be done continuously so that a predetermined percentage of catalyst is removed and replenished on a continuous basis.
  • the catalyst particles (625) will vary in size and shape, each having a different settling velocity. Therefore, the preferred lignin conversion products removal velocity is less than the settling velocity of at least 75% by weight of the catalyst particles, with a lignin conversion products removal velocity less than the settling velocity of at least 85% by weight of the catalyst particles being more preferred, with a lignin conversion products removal velocity less than the settling velocity of at least 90% by weight of the catalyst particles being even more preferred, with a lignin conversion products removal velocity less than the settling velocity of at least 95% by weight of the catalyst particles being yet even more preferred, with a lignin conversion products removal velocity less than the settling velocity of 100% by weight of the catalyst particles being most preferred.
  • the "75% by weight of the catalyst particles” means that 75% by weight of the total amount of catalyst in the reactor remains in the reactor and 25% by weight of the total amount of the catalyst in the reactor is removed. Alternatively, the percent equals
  • R is the weight of the catalyst remaining
  • X is the weight of the catalyst exited or removed from the reactor. The 100 is to make the number a percent.
  • De-ionized water was added to a lignin-rich composition obtained from the pretreatment of ligno-cellulosic biomass to obtain a slurry comprised of lignin having a dry matter content of 20 weight percent of the mass of the slurry.
  • the mixture was inserted into a blender (Waring Blender, model HGBSSSS6) and thoroughly mixed intermittently for 10 min. to reach a homogenous slurry. The homogeneity of the slurry was evaluated by eye.
  • the slurry was inserted into a mix tank (340) with constant agitation.
  • the mix tank (340) was a stainless steel, dish bottom tank with a bottom discharge port connected to a Chandler Quizix QX dual syringe pump having two pump cavities.
  • Inlet valves (350) were inserted between the mix tank (340) and the two pump cavities of the Chandler Quizix QX dual syringe pump.
  • the Chandler Quizix QX dual syringe pump was connected by tubing to a Parr 4575 reactor equipped with a dual 45° pitched turbine blade, cooling coil, separate gas and slurry feed ports and a stainless steel discharge dip tube (610) having an outside diameter of 0.25 inches and an inside diameter of 0.152 inches.
  • Outlet valves were inserted between the two pump cavities of the Chandler Quizix QX dual syringe pump and the Parr reactor.
  • the lignin conversion reactor pressure was controlled by a Mity Mite Model 91 Back Pressure Regulator (BPR) positioned in the lignin conversion reactor discharge line between the Parr reactor and the products receiver.
  • BPR Back Pressure Regulator
  • the lignin conversion pressure was measured by means of a pressure transducer (Ashcroft Type 62) connected to the Parr reactor.
  • the Parr reactor was charged with 150 mL of de-ionized water prior to beginning the experiments.
  • the lignin conversion reactor pressure was increased to 48.3 bar by way of 20° C hydrogen.
  • the lignin conversion reactor was heated to 90% of the lignin conversion temperature prior to charging the slurry comprised of lignin to the lignin conversion reactor.
  • additional de- ionized water was passed from the mix tank (340) through the Chandler Quizix QX dual syringe pump into the lignin conversion reactor (500) at a rate of 2.8 mL/min. Hydrogen flow was added to the lignin conversion reactor at a rate of 150 seem.
  • the temperature in the lignin conversion reactor was increased to 100% of the lignin conversion temperature, and the lignin conversion reactor pressure was adjusted via the BPR to the desired operating pressure as reflected in the experiments.
  • Slurry comprised of lignin was then charged to the reactor through the Chandler Quizix QX dual syringe pump at a rate of 2.8 mL/min.
  • the slurry comprised of lignin was passed from the mix tank (340) through the Chandler Quizix QX dual syringe pump and into the Parr reactor by opening and closing the inlet valves (350) and outlet valves (450) in a manner that allowed the lignin slurry to pass continuously into the Parr reactor.
  • the lignin conversion products were continuously removed from the lignin conversion reactor (500) via the dip tube (610) and cooled to approximately 35°C before passing through the BPR. After passing through the BPR, the lignin conversion products were collected in a stainless steel products receiver fitted with a vent line to allow non-condensable gases from the lignin conversion reactor to separate from the liquid lignin conversion products.
  • the lignin conversion reactor was allowed to reach steady state conditions, and after four reactor residence cycles, the lignin conversion products were collected in the products receiver for approximately one additional reactor residence cycle. At this time, all feed streams to the lignin conversion reactor were stopped, and the lignin conversion reactor was isolated from the products receiver by way of an isolation valve. The lignin conversion reactor was cooled to approximately 30°C and the pressure was reduced to atmospheric pressure by opening a vent valve.
  • liquid lignin conversion products were mixed with an equal amount of methyl tertiary butyl ether (MTBE). This mixture was filtered through a Buchner funnel fitted with a Whatman #1 filter paper.
  • MTBE methyl tertiary butyl ether
  • sponge nickel catalyst was added directly to the slurry comprised of lignin resulting in a slurry comprised of 13.5 weight percent lignin on a dry basis and 7.0 weight percent sponge nickel catalyst on a dry basis.
  • the sponge nickel catalyst had a particle size range of between 10 and 40 ⁇ .
  • the lignin conversion reactor was operated at 340°C and 156.4 bar, which is approximately 10 bar above the vapor pressure of water at 340°C. At operating conditions, the average residence time of the slurry comprised of lignin was 53 minutes. Surprisingly, after the experiment was stopped and the liquid lignin conversion products were filtered, very little catalyst was observed on the filter paper, and in one instance, no catalyst was observed at all. Where catalyst was observed on the filter paper, it was observed as fine particles of catalyst. When the Parr reactor was shut down and opened, it was surprisingly observed that nearly all of the catalyst remained in the lignin conversion reactor.
  • the settling velocity of the catalyst particles is greater than the velocity of the removal of lignin conversion products from the lignin conversion reactor (500) through the dip tube (610). This results in the surprising and advantageous retention of catalyst in the lignin conversion reactor. It is further believed that the fibrous, VelcroO-like nature of the lignin- rich composition in the slurry comprised of lignin will attach itself to the catalyst particles (625) and remove them from the lignin conversion reactor where lower levels of lignin conversion are achieved.
  • all or a portion of the catalyst can be removed from the Parr reactor by decreasing the diameter and length of the dip tube, thereby increasing the velocity of the removal of lignin conversion products from the Parr reactor to a level greater than that of the settling velocity of the catalyst.
  • the process can be operated where the lignin conversion reactor is a continuous stir tank reactor (CSTR), the CSTR requires a high amount of energy input, and the high pressure required to convert lignin on a continuous basis results in an unreasonably large reactor when utilizing a CSTR. It has been discovered that a bubble column reactor requires less energy input and allows for a smaller reactor for a continuous lignin conversion process.
  • CSTR continuous stir tank reactor
  • a bubble column reactor consists of at least one vertical cylinder at least partially filled with liquid. Gas is fed to the bottom of the cylinder through a gas feed tube causing a turbulent upward stream of bubbles.
  • the gas may be hydrogen or nitrogen.
  • the liquid may comprise water.
  • the liquid may comprise a hydrogen donor. The gas flow could be nitrogen or hydrogen gas, at a sufficient rate to keep the catalyst particles fluidized within the liquid components of the reactor.
  • the bubble column reactor will also comprise a gas distributor at the bottom of the vertical cylinder to allow for even distribution of gas bubbles.
  • a preferred gas distributer is comprised of a material which is not corroded by the reactants, such as a stainless steel mesh.
  • a slurry comprised of lignin can be fed to the bottom of the vertical cylinder through a slurry feed tube.
  • the amount of slurry comprised of lignin fed to the bubble column reactor can be varied to achieve increased rates of lignin conversion as described in the experimental section below based on temperature, pressure, hydrogen flow, amount of catalyst and residence time.
  • a plurality of catalysts may be charged to the bubble column reactor through the slurry feed tube. In another embodiment a plurality of catalysts may be charged directly to the bubble column reactor prior to charging the hydrogen and/or slurry comprised of lignin to the bubble column reactor.
  • the reactor scheme for the bubble column may also include a second column for the disengagment of the solid unreacted lignin and catalyst to flow by gravity into the bottom of the bubble column or ebullating reactor and be recontacted with fresh gas.
  • the bubble column reactor may also comprise a heating element which allows for regulation of the bubble column reactor temperature.
  • this heating element comprises a plurality of heating coils wrapped around the vertical cylinder.
  • the bubble column reactor temperature is between 220°C and 350°C.
  • the reactor conditions of pressure and temperature should be selected so as to prevent char formation as discussed earlier.
  • Bubble column reactor pressure may be varied based upon the bubble column reactor temperature and gas flow rate as described in the experimental section below.
  • the bubble column reactor pressure is between 150 bar and 230 bar.
  • a dip tube may be inserted at the top of the vertical cylinder for removing a plurality of the lignin conversion products to a products receiver.
  • the bubble column reactor may consist of a plurality of vertical cylinders, each having a separate gas feed tube, a separate slurry feed tube and a separate dip tube. What was found is that, by utilizing a bubble column reactor instead of a CSTR, significant amounts of energy savings can be attained due to the lack of a separate stirring element. Additionally, the bubble column results in higher rates of conversion than a CSTR while converting the slurry comprised of lignin to similar products.
  • De-ionized water was added to a lignin-rich composition obtained from the pretreatment of ligno-cellulosic biomass to obtain a slurry comprised of lignin having a dry matter solids content of 5 weight percent of the mass of the slurry comprised of lignin.
  • the mixture was inserted into a blender (Waring Blender, model HGBSS6) and thoroughly mixed intermittently at thirty second intervals (thirty seconds of mixing followed by thirty seconds without mixing) for 10 min. to reach a visually homogenous slurry. (See Experimental establishing the ability of the Waring HGBSS6 Blender to homogenously disperse on a quantitative basis). The homogeneity of the slurry comprised of lignin was evaluated by eye.
  • the slurry comprised of lignin was inserted into a mix tank with constant agitation.
  • the mix tank was a stainless steel, dish bottom tank with a bottom discharge port connected to a Chandler Quizix QX dual syringe pump having two pump cavities. Inlet ball valves were inserted between the mix tank and the two pump cavities of the Chandler Quizix QX dual syringe pump.
  • the Chandler Quizix QX dual syringe pump was connected by stream (1510) to a bubble column reactor having an inside diameter (1540) of one inch, a height (1545) of thirty inches, a heating element (1550), a gas distributor (1570) comprised of stainless steel mesh having a length of two inches, a slurry feed tube (1560) at the bottom of the column having a length of six inches for feeding the lignin slurry to the bubble column reactor, and a dip tube (1565) having a length of eight inches connected to a transfer line (1580) at the top of the bubble column reactor for removal of reaction products to a products receiver.
  • the products receiver was maintained at the same pressure as the bubble column reactor.
  • the bubble column reactor further contained a vent (1520) connected to a rupture disk (1521) and a pressure transducer (1522).
  • the bubble column reactor further contained a thermal well (1590) for measuring temperature inside the bubble column reactor during the experiment.
  • the slurry comprised of lignin was passed from the mix tank through the Chandler Quizix QX dual syringe pump and into the bubble column reactor by opening and closing the inlet and outlet valves in a manner that allowed the lignin slurry to pass continuously into the bubble column reactor.
  • the total amount of slurry comprised of lignin passed through the system was 45 g.
  • 11.1293 g of un-reacted slurry comprised of lignin remained in the bubble column reactor, however, in removing the un-reacted slurry comprised of lignin from the bubble column an unknown quantity was spilled.
  • lignin conversion products were phenol oils that were nearly identical in composition as measured by G.C. Mass Spectrometer to the phenol oils produced during a lignin conversion process in a continuous stir tank reactor (CSTR) (See Figure 9). Conversion rate of the slurry comprised of lignin was 75.27%, not taking into account the unknown quantity of un-reacted slurry comprised of lignin which was spilled.
  • Bubble Column Experiment 4 For Experiment 4, the inventors increased the bubble column reactor pressure from 166.49 bar to 172.4 bar and reduced the rate of slurry flow from 3 mL/min to 2 mL/min. Total run time was increased to six hours and forty minutes, and total input of the slurry comprised of lignin was decreased to 40 g. The number of turns of slurry comprised of lignin through the bubble column reactor decreased to 3.62. The total amount of slurry comprised of lignin present in the bubble column reactor after reaching assumed steady state during the experiment was 18.4116 g. All other conditions remained the same as in Experiment 2. When the inventors concluded the experiment, 18.4116 g of un-reacted slurry comprised of lignin remained in the bubble column reactor.
  • the products receiver was de-pressurized and discharged. After four hours, the products receiver contained 0.89 g of phenol oils. After eight hours the products receiver contained 3.25 g of phenol oils. After ten hours the products receiver contained 0.97 g of phenol oils. Upon completion of the experiment, it was further observed that 2.4 g of phenol oils remained present in the transfer line. When the residual solids were drained from the bubble column reactor, filtered, washed with acetone and Rotovapped, it was further observed that 1 g of phenol oils was present in the residual solids.
  • the products receiver was de-pressurized and discharged. After two hours forty minutes the products receiver contained 1.43 g of phenol oils. After five hours twenty minutes the products receiver contained 3.27 g of phenol oils. After eight hours the products receiver contained 2.64 g of phenol oils. After ten hours forty minutes the products receiver contained 4.7 g of phenol oils. After twelve hours the products receiver contained 3.57 g of phenol oils. Upon completion of the experiment, it was further observed that 9.29 g of phenol oils remained present in the transfer line.
  • the inventors increased the bubble column reactor temperature to 335° C resulting in an increased bubble column reactor pressure of 207.9 bar.
  • the inventors also increased the amount of catalyst charged to the bubble column reactor to 85 g and the rate of slurry flow from 2 mL/min to 3 mL/min. Total run time was decreased to five hours. This resulted in a decreased total input of slurry comprised of lignin of 45 g.
  • the number of residence cycles of slurry comprised of lignin through the reactor decreased to 4.3.
  • the total amount of slurry comprised of lignin present in the bubble column reactor at any one time during the experiment was 12.082 g. All other conditions remained the same as in Experiment 6. When the inventors concluded the experiment, 12.082 g of slurry comprised of lignin remained in the bubble column reactor.
  • the products receiver was de-pressurized and discharged. After two hours the products receiver contained 2.69 g of phenol oils. After four hours the products receiver contained 1.34 g of phenol oils. After five hours the products receiver contained 0.36 g of phenol oils. Upon completion of the experiment, it was further observed that 11.92 g of phenol oils remained present in the transfer line. When the residual solids were drained from the bubble column reactor, filtered, washed with acetone and Rotovapped, it was further observed that 1.25 g of phenol oils was present in the residual solids.
  • Total slurry comprised of lignin in the bubble column reactor is equivalent to the amount of unconverted lignin slurry remaining in the bubble column reactor upon shutdown.
  • BC1 11.1293 g of unconverted lignin remained in the bubble column reactor, however an unknown quantity of un-reacted lignin was spilled upon removal from the bubble column reactor at the end of the Experiment resulting in inaccurate measurements.
  • the lignin conversion process is considered a continuous process because the lignin conversion products are removed from the lignin conversion reactor (500) in a continuous manner.
  • the reactants such as the component of the slurry comprised of lignin are generally introduced into the lignin conversion reactor in a continuous manner as well.
  • a continuous manner does not mean that that feedstock or products are continuously introduced or removed at the same rate.
  • the slurry comprised of lignin is introduced into the lignin conversion reactor (500) in steady aliquots or pulses. Thus there are moments, when there is no product entering the lignin conversion reactor.
  • the mass introduced into the lignin conversion reactor equals the mass removed from the lignin conversion reactor.
  • One distinguishing feature between a continuous and a batch process is that, in the continuous process, the reaction is occurring or progressing at the same time that either the reactant feeds are introduced into the lignin conversion reactor and/or the lignin conversion products are removed from the lignin conversion reactor.
  • Another way to state this that the conversion (e.g. deoxygenating, or hydrogenating) in the lignin conversion reactor occurs while simultaneously, or at the same time, removing at least a portion of the lignin conversion products from the lignin conversion reactor. Such removal is done in a continuous manner which includes a pulse removal.
  • the invented process converts the lignin in the feedstock to several different product types. As described later, the process conditions can be set to produce one class of compounds at the expense of another class of compounds.
  • the lignin conversion can be considered as a deoxygenation of lignin.
  • the lignin will not convert to a single product, but to a plurality of lignin conversion products.
  • the feedstock comprising lignin is exposed to additional hydrogen (H 2 ) gas which can be added in the conventional manner according to the temperature and pressure of the lignin conversion reactor.
  • the plurality of lignin conversion products may be void of ethylene glycol or propylene glycol.
  • first catalyst present in the lignin conversion reactor (500).
  • the reason it is called a first catalyst is that there may be a second catalyst added to the lignin conversion reactor or a second catalyst may be used to further react the lignin conversion products in a different step. While there may be a second catalyst, it is possible in one embodiment that there is only one catalyst, the first catalyst.
  • the lignin conversion reactor may be void a second catalyst.
  • the lignin conversion products may comprise compounds which are found in jet fuel, or the lignin conversion products may be further converted to compounds comprising jet fuel.
  • the first catalyst can be any one of the catalysts known to catalyze the reaction of hydrogen with lignin.
  • the first catalyst used in the conversion process is preferably a sponge elemental metal catalyst comprising at least one sponge elemental metal created by the Raney process as described and claimed in US 1,628,190, the teachings of which are incorporated in their entirety.
  • the process as claimed creates an alloy of at least a first metal and a second metal dissolves the second metal out of the first metal, leaving behind a finely divided elemental first metal with high surface area. This high surface area is often described as a sponge structure.
  • the preferred first catalyst of the lignin conversion process is known as Raney Nickel, or where the finely divided elemental metal is nickel.
  • Another preferred metal is a metal selected from the group consisting of palladium, platinum, nickel, ruthenium, rhodium, molybdenum, cobalt, and iron. Because water is a feature of the reaction, the catalyst structure, particularly its support must be hydrothermally stable. Due to the heterogeneous nature, at least a portion of the first catalyst is present as a plurality of particles, or in particle form. At a least a portion of the first catalyst, if not all of the first catalyst, is not present as a fixed bed.
  • the first catalyst may or may not be supported or unsupported, but is generally not present as a fixed bed. If a fixed bed catalyst is used, the feedstock should be present as a liquid as opposed to a slurry so that solids do not plug the pores of the fixed bed.
  • the contemplation of a fixed bed is part of the conception because it is believed that many of the enabling principles of this process are applicable to both a slurry feedstock and a liquid feedstock without solids, or at least less than 1 % solids by weight, of a slurry where the solids are present in a size less than the pores of the fixed bed.
  • the amount of the first catalyst can be expressed by the weight of the elemental nickel to the dry weight of the lignin feedstock, where the weight of the elemental nickel to the dry weight of the lignin in the feedstock should be in the range of about 0.25 to about 2.0, with the range of about 0.3 to about 1.5 being more preferred with at least about 0.5 to 1.0 being the most preferred.
  • the process is void of a catalytic amount of a second catalyst.
  • the second catalyst can be any of the standard hydrogenation catalysts known, with the preferred second catalyst being the same as the first catalyst.
  • the amount of the second catalyst is the same as the amount of the first catalyst.
  • the preferred third catalyst is a Zeolite creating heterogeneous cites for the reactions to progress in an acidic environment.
  • sponge elemental metal catalysts created by the Raney process can be used in this process, they have many disadvantages.
  • Sponge elemental metal catalysts created by the Raney process such as Raney Nickel, require extreme precautions before, during and after the reaction.
  • Raney Nickel in particular is a pyrophoric catalyst, and must be maintained in an aqueous environment in order to avoid spontaneous combustion.
  • the catalyst comprises a crystalline metal oxide catalyst.
  • Crystalline metal oxide catalysts are not pyrophoric catalysts, and can be handled in ambient conditions unlike Raney Nickel which requires special handling conditions and storage in an aqueous environment.
  • the crystalline metal oxide catalyst may be a crystalline mono-metallic oxide catalyst or a crystalline bi-metallic oxide catalyst.
  • the crystalline metal oxide catalyst is in nanoparticle form having an average crystallite particle size of less than 250 nm, with an average crystallite particle size of less than 150 nm being more preferred, an average crystallite particle size of less than 100 nm being even more preferred and an average crystallite particle size of less than 50 nm being most preferred.
  • the metal may be selected from the group consisting of Cesium, Copper, Nickel, Iron, Zinc and Cobalt.
  • One preferred crystalline mono-metallic oxide catalyst is nickel oxide.
  • the crystalline metallic oxide catalyst is a crystalline bi-metallic oxide catalyst.
  • Crystalline bi-metallic oxide catalyst can be obtained from any of the known processes, and those yet to be discovered.
  • a crystalline mono-metallic oxide catalyst such as nickel oxide
  • a second metal such as zinc, iron or cobalt.
  • some of the metal species of the crystalline mono-metallic oxide catalyst are replaced with a different metallic species, resulting in a crystalline bi-metallic oxide catalyst.
  • the crystalline mono-metallic oxide catalyst may be doped with one or more than one metal.
  • the crystalline mono-metallic oxide catalyst may be doped with zinc and iron metal oxides.
  • the catalyst is a crystalline bi-metallic oxide catalyst
  • the catalyst will be comprised of at least two metals, wherein at least one of the metals is selected from the group consisting of Platinum, Palladium, Cesium, Copper, Nickel, Ruthenium, Rhodium, Gold, Iron, Cobalt and Iridium.
  • Preferred bi-metallic oxide catalysts include bi-metallic catalysts comprising nickel oxide doped with at least one element selected from the group consisting of zinc, iron and cobalt.
  • the crystalline metal oxide catalyst is present as free particles. In another embodiment, at least a portion of the crystalline metal oxide catalyst may be present in a fixed bed catalytic process.
  • the crystalline metal oxide catalyst will convert lignin to useful compounds in a liquid solvent.
  • the liquid solvent is water.
  • the liquid solvent is an organic solvent such as methanol.
  • Crystalline metal oxide catalysts also demonstrate high yield conversion of lignin to phenolic compounds, and are highly selective towards functionalized phenols. Experiments were run demonstrating the ability of crystalline metal oxide catalysts to convert lignin to phenolic compounds.
  • the pre-treated lignin feedstream and sufficient water from a source other than the pre-treated lignin feedstream to reach a dry matter concentration of 5 weight percent were inserted along with a catalyst in a 50 mL parr mini reactor. After the materials were inserted into the reactor, the reactor was pressurized to about 15 bar with nitrogen, stirred for five minutes, and vented. The purging cycle was repeated two more times and then two times with hydrogen. Finally, the reactor was pressurized at 25 °C to a hydrogen pressure of 200 psi and then heated with an electric to the reaction temperature. Once the internal temperature of the reactor was stabilized, the reactor was stirred for the reaction time of 60 minutes.
  • the heating element was removed and the reactor was allowed to cool using an ice bath. Once the reactor was cooled to a temperature of 24° C, the gas sample was collected for further analysis and the reactor was vented until the pressure in the reactor was reduced to 0 psi.
  • Nanoparticles of nickel oxide were used as a catalyst. Average particle size of the nickel oxide catalyst particles was reported from the manufacturer Sigma- Aldrich Co., LLC from St. Louis, Missouri, USA. In certain experiments the nanoparticles of nickel oxide were reduced to metallic nickel in hydrogen at 400° C for two hours prior to charging to the reactor. In other experiments the nanoparticles of nickel oxide were not reduced in hydrogen prior to charging to the reactor.
  • reaction products were removed and analyzed to determine the amount of lignin that was converted and the yield of phenols in the conversion products.
  • the conversion rate was determined by filtering the reaction mixture, and the filtered solution was extracted using dichloromethane. The remaining organic layer was rotovapped, and the remaining solids were ashed to determine the conversion percentage of the process. The remaining conversion products were sent for GC/MS analysis to determine the yield of phenols and the type of phenols produced.
  • the Inventors used reduced nanoparticles of nickel oxide as a catalyst.
  • 0.8 g of catalyst was charged to the reactor along with 1.5 g of lignin in the form of a lignin slurry.
  • the solvent used to create the slurry was deionized water.
  • the reactor was heated to a reaction temperature of 305° C and time zero was started.
  • the reactor was further pressurized to a reaction pressure of 200 psi with hydrogen gas.
  • the profile of the reaction products showed that 83.0% of the lignin charged to the reactor was converted. This demonstrated that nanoparticles of nickel oxide could be utilized as a catalyst for the conversion of lignin.
  • GC/MS of the reaction products indicates that the nanoparticles of nickel oxide demonstrate high selectivity towards "light” phenols as opposed to "heavies", heavies being defined as molecules having long and short chain hydrocarbons as side products.
  • the reaction products showed that 68.8% of the lignin charged to the reactor was converted. Also, the reaction products showed that 25.0% of the 68.8% of the lignin that was converted was converted to phenols. Again, it is important to note here that only 55% of the pre-treated lignin feedstream comprises lignin. This is an increase of 8.4% yield over the reduced nanoparticles of nickel oxide. This demonstrates that, while the unreduced nanoparticles of nickel oxide may not provide similar conversion rates to the reduced nanoparticles of nickel oxide, the unreduced nanoparticles of nickel oxide are yielding a higher percentage of phenols relative to the amount of lignin converted.
  • GC/MS of the reaction products further indicates that the unreduced nanoparticles of nickel oxide demonstrate similar selectivity away from heavies and towards "light" phenols as the reduced nanoparticles of nickel oxide.
  • reaction products showed that 61.8 % of the lignin charged to the reactor was converted, but that, of that 61.8 %, 23.3% had been converted to phenols. This demonstrates that, while decreasing the amount of unreduced nanoparticles of nickel oxide may decrease the amount of lignin converted, it does not significantly reduce the yield of phenols found in the converted lignin.
  • reaction products showed that 72.0 % of the lignin charged to the reactor was converted, but that, of that 72.0 , only 19.4 % had been converted to phenols. This demonstrates that, while increasing the reaction temperature may increase the amount of lignin converted, it has a negative impact on the yield of phenols found in the converted lignin.
  • reaction products showed that 75.7 % of the lignin charged to the reactor was converted, but that only 10.6 % of the converted lignin was phenols. This demonstrates the need for nanoparticles of nickel oxide as opposed to macroparticles of nickel oxide when seeking to convert lignin to phenols.
  • the Inventors obtained nanoparticles of nickel oxide which had been doped with other metal oxides (crystalline bi-metallic oxide catalysts). Average particle size was reported by the manufacturer Sigma-Aldrich Co., LLC from St. Louis, Missouri, USA. Operating conditions and conversion data for nanoparticles of nickel oxides doped with other metals are reported below in Table 6. Operating conditions and conversion data for Experiment 4 are included for comparison of the nanoparticles of nickel oxides doped with other metals to those that have not been doped with other metals.
  • Ni-CoO nickel cobalt oxide nanopowder
  • reaction products showed that 68.7% of the lignin had been converted, and that 23.2% of the converted lignin were phenols.
  • GC/MS of the reaction products further indicates the selectivity towards "light" phenols as seen in Experiment 4. This demonstrates that there is no significant difference in the conversion percentage, yield of phenols or type of phenols produced between nanoparticles of nickel oxide and nanoparticles of nickel oxide doped with cobalt oxide.
  • reaction products showed that 67.8 % of the lignin had been converted, but that only 17.3 % of the converted lignin was phenols.
  • GC/MS of the reaction products further shows selectivity towards "light" phenols as seen in Experiment 4. This demonstrates that nanoparticles of nickel oxide doped with iron oxide do not function as well for converting lignin to phenols as nanoparticles of nickel oxide.
  • Ni-Zn-FeO nickel zinc iron oxide nanopowder
  • reaction products showed that 67.8% of the lignin had been converted, and that, surprisingly 37.2 % of the converted lignin was phenols.
  • GC/MS of the reaction products further indicates that the selectivity towards "light" phenols as seen in Experiment 4. The demonstrates that nanoparticles of nickel oxide doped with zinc and iron are highly desirable when seeking to convert lignin to phenols.
  • the converted lignin feedstream may be further converted to an aromatic converted lignin product.
  • the converted lignin feedstream suitable for this process will comprise products derived from the lignin of ligno-cellulosic biomass.
  • the product derived from the lignin of a lingo- cellulosic biomass is a phenol oil which is the term used to describe the composition consisting of all of the phenols in the converted lignin feedstream.
  • the converted lignin feedstream is combined with one species or multiple species of molecules.
  • These hydrogen donor molecules, considered reactants may be selected from the group consisting of hydrogen donor molecules produced from a previously converted lignin feedstream, hydrogen donor molecules derived from a source other than a product stream from a previously converted lignin feedstream and mixtures thereof.
  • a hydrogen donor molecule donates at least one hydrogen atom, both of which are consumed during the process.
  • the hydrogen donor molecule can be selected from the group consisting of sorbitol, glycerol, xylitol and ethylene glycol.
  • Another group of hydrogen donor molecules are those molecules having the formula of:
  • Ri is selected from the group consisting of -OCH 2 , -H, and -OH and R 2 is selected from the group consisting of -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , and -CH 2 -CH 2 -CH 2 -CH 3 .
  • Another group of hydrogen donor molecules are those molecules having the formula of:
  • R is selected from the group consisting of -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , and -CH 2 - CH 2 -CH 2 -CH 3 .
  • the hydrogen donor molecules are preferably not molecules that produce an aldehyde as one of the final conversion products of the donation process. Terminal alcohols like methanol and propanol molecules produce an aldehyde as one of the final conversion products of the donation process. It is preferred that the hydrogen donor molecules do not produce an aldehyde as one of the final conversion products of the donation process because the aldehyde creates side products in later processing.
  • the hydrogen donor molecules can also be supplied from a product stream from a previously converted lignin feedstream wherein the product stream includes cyclohexanol and substituted cyclohexanols.
  • Hydrogen donor molecules selected from a source other than the products from a previously converted lignin feedstream include isopropanol, ethylene glycol, glycerol, cyclohexanol and substituted cyclohexanols. In a more preferred embodiment the hydrogen donor molecule is isopropanol.
  • the plurality of hydrogen donor molecules comprise a mixture of cyclohexanol and substituted cyclohexanols from the product of a previously converted lignin feedstream and cyclohexanol and substituted cyclohexanols from a source other than the product of a previously converted lignin feedstream.
  • the hydrogen donor molecule is cyclohexanol and substituted cyclohexanols derived from and separated from the converted lignin feedstream during an earlier process.
  • the hydrogen donor molecule is present with water as well.
  • the required amount of hydrogen donor molecules or mixture thereof can be determined by the mole ratio of moles of hydrogen donor molecule(s) to moles of phenol oil where the phenol oil is assigned an average molecular weight of 150 g/mol.
  • the mole ratio of moles of hydrogen donor molecule(s) to moles of phenol oil should preferably be in the range of between 2.0:1.0 and 10.0: 1.0 with a range of between 3.0:1.0 and 9.0:1.0 being more preferred, a range of between 4.0:1.0 and 8.0: 1.0 being even more preferred and a range of between 5.0: 1.0 and 7.0:1.0 being most preferred.
  • H 2 gas The role of H 2 gas has been found to act as a poison to the conversion to aromatics.
  • the amount of H 2 gas, if added to the reaction, should be kept at less than 25% of the total amount of hydrogen atoms [H] and H 2 molecules used in the process representing the following formula:
  • the converted liquid feedstream and hydrogen donor molecules are exposed to a metal catalyst, preferably a Nickel containing catalyst.
  • a metal catalyst preferably a Nickel containing catalyst.
  • nickel containing catalysts are described herein and include the heterogeneous Raney Nickel catalysts and heterogeneous and homogeneous Nickel Oxide catalysts.
  • the ratio of mmol of hydrogen donor molecules to mmol of catalyst metals is preferred to be in the range of between 1.0: 1.0 and 5.0:1.0 with a range of between 1.2:1.0 and 4.0:1.0 being more preferred and a range of between 1.5:1.0 and 3.0:1.0 being most preferred. Only the mmol of metals in the catalyst are used to calculate the mmol of catalyst.
  • the materials are exposed to each other at a reaction temperature in the range of 190° C to 350° C, with 200° C to 310° C being more preferred, with 210° C to 300° C being even more preferred and 210° C to 280° C being the most preferred.
  • the reaction time depends upon the amount of catalyst by weight, the reaction temperature and the moles of hydrogen donor molecules (not H 2 gas). Generally this is in the range of 15 minutes to 6 hours, but times of 10 minutes to 15 hours are conceivable.
  • the process can be run in both batch and continuous mode.
  • continuous mode the product is being removed from the reaction vessel while the reaction is occurring.
  • examples were produced on a continuous stirred thermal reactor, a CSTR, although any reactor capable of removing product from the reaction vessel while the reaction is occurring can be used for a continuous process.
  • Another carbohydrate conversion step and embodied in Figure 1 is to create a slurry lignin feedstock comprised of carbohydrates and lignin, feed it to a carbohydrate conversion reactor as described in United States Patent Publication Numbers US2011/312487, US2011/312488 and US2011/0313212 by pressuring the slurry feedstock as described in this specification and feeding into a first reaction zone and
  • the catalyst in the consists essentially of at least two active metal components selected from the group consisting of: (i) Mo, W, V, Ni, Co, Fe, Ta, Nb, Ti, o, Zr and combinations thereof wherein the metal is in the elemental state or the metal is a carbide compound, a nitride compound, or a phosphide compound;
  • the mmol of Phenol Oil is calculated as follows:
  • the amount of phenol oil consists of all of the phenols (typically 5 different types of phenol units are present but with similar backbone alkyl phenol unit).
  • the phenol oil has an assigned average molecular weight of 150.0 g/mol which is used as the repetitive unit when calculating the amount of mmol of phenol oil in the crude mixture, so 5.0g phenol oil has 33.3 mmol of phenols.
  • Table 7a is the gross characterization of the batch process operated on a feedstream derived as described above.
  • the reaction conditions in the batch process was to use 2.0mmol of phenol oil for every l.Og wet Raney Ni 2800 having a 1:1 ratio by weight of nickel to H 2 0.
  • Table 7b is the gross characterization of the feeds and prior art lower temperatures as indicated in the Table 7b.
  • the reaction conditions according to the prior art was 0.2 g of a Model Phenol Compound Feed and 1.0 g wet Raney Ni 2800 having a 1 :1 ratio of grams of nickel to grams of H 2 0.
  • aromatics comprised 48.97% of the products when ethylene glycol was the hydrogen donor.
  • benzene is 15% of the aromatics when cyclohexanol is the donor.
  • EGiethylene glycol IPA:Isopropyl alcohol; CHicyclohexanol; GY:glycerol; Bibenzene; Titoluene; EBiethylbenzene; PBipropylbenzene; X: xylenes; CA: Cycloalcohols; CK: Cycloalkanes
  • Hydrogenated Products (%) is the percent of the converted products which are hydrogenated.
  • Feed Composition 15 wt% Phenol Oil in Isopropanol (14.0:1 .0 mol ratio H-Donor to Phenol Oil,
  • Catalyst Amt 85 g wet Grace 2800 Raney Ni
  • H-Donor Isopropanol Total Reactor Volume 500 ml
  • Feed Composition 15 wt% Phenol Oil in Isopropanol (14.0:1 .0 mol ratio H-Donor to Phenol Oil,
  • Catalyst Amt 85 g wet Grace 2800 Raney Ni
  • Feed Composition 10 wt% Phenol Oil in Cyclohexanol (13.3:1 .0 mol ratio H-Donor to Phenol Oil,
  • Catalyst Amt 50 g wet Grace 2800 Raney Ni
  • Feed Composition 10 wt% Phenol Oil in Cyclohexanol (13.3:1 .0 mol ratio H-Donor to Phenol Oil,
  • Catalyst Amt 50 g wet Grace 2800 Raney Ni
  • H-Donor 4-Methylcyclohexanol
  • Feed Composition 9 wt% Phenol Oil in 4-Methylcyclohexanol ( 3.1 :1 .0 mol ratio H-Donor to
  • Catalyst Amt 50 g wet Grace 2800 Raney Ni
  • H-Donor 4-Methylcyclohexanol
  • Feed Composition 9 wt% Phenol Oil in 4-Methylcyclohexanol (13.1 :1 .0 mol ratio H-Donor to
  • Catalyst Amt 50 g wet Grace 2800 Raney Ni
  • Table 9 shows the difference between the batch and CSTR reaction processes.
  • the above process can be preceeded by a carbohydrate conversion process which is fed by ligno-cellulosic biomass.
  • the above process can use a feedstock from a commercial lignocellulosic ethanol plant, but at the same time is flexible enough to use lignin-containing raw materials from other processes.
  • the current raw material is derived from a naturally occurring lignocellulosic biomass, after the majority of the carbohydrate fraction has been biologically converted to ethanol.
  • the sulfur content of the feedstock is near to zero, and consequently no desulfurization is required to obtain jet fuels (in contrast to a fossil feedstock).
  • the lignin co-product is collected after distillation and used as boiler fuel to generate steam and power. This is not necessarily the best use of these lignin rich residues (LRR).
  • the envisioned process is one in which the biorefinery produces ethanol (or some other product) from the carbohydrate fraction of the ligno-cellulosic biomass while the LRR is utilized as a feedstock for fuels and chemicals produced using at least the above process if not others for lignin conversion.
  • ethylene glycol used in the hydrogen donor solvent process would come from the conversion of the carbohydrates to ethylene glycol as described in the art. Other alcohols are well known as well.
  • the carbohydrate conversion could be catalytic or enzymatic. Because the lignin conversion process does not use pure hydrogen donors, the need to purify the carbohydrate conversion products, such as ethylene glycol is not necessary.
  • the plurality of conversion products preferably comprise at least one product selected from the group consisting of carbon dioxide, methane, ethane, phenols, benzene, toluene, and xylenes.
  • Another embodiment of the process is that the plurality of lignin conversion products are cooled after leaving the reactor separating the vapor from the liquid and solids, with the back pressure regulator (700) located after the liquid solids separator (600), the pressure of the lignin conversion process can now be controlled.
  • the temperature of the lignin conversion products generated by the lignin conversion process are substantially greater than the temperature of the steam, soaking and fermentation processes of the pre-treatment and carbohydrate conversion processes that would precede the lignin conversion process.
  • the inventors clearly contemplate that in the integrated or co-sited operation that the heat from the lignin conversion products would be transferred to soaking, steam pretreatment, hydroylsis, and/or fermentation processes of the pre-treatment process.
  • liquid lignin conversion products are obtained, they can then be subsequently converted to a number of different chemical feedstocks and intermediates.
  • One preferred intermediate is at least one polyester intermediate selected from the group consisting of ethylene glycol, terephthalic acid, and isophthalic acid. Once the intermediate is made, the conversion of the intermediate to polyester and subsequent articles such as soft drink bottles, beer bottles, and other packaging articles can be accomplished using the conventional techniques known today and those yet to be invented.
  • the carbohydrate conversion products are selected from the group consisting of alcohols, polyols, glucans, gluco-lignins and cellulose.
  • Fermentation is one such carbohydrate conversion step.
  • Another carbohydrate conversion step and embodied in Figure 1 is to create a slurry feedstock comprised of carbohydrates and lignin, feed it to a carbohydrate conversion reactor as described in US2011/312487 and US2011/312488 and US2011/0313212 by pressuring the slurry feedstock as described in this specification and feeding it into a first reaction zone and
  • the secondary feedstock stream comprising lignin can be again optionally pressurized and fed into the lignin conversion reactor (500) to convert lignin into the phenols and other component in the plurality of lignin conversion products.
  • the polyols such as ethylene glycol and propylene glycol may be used as a hydrogen donor to convert the lignin to lignin conversion products.
  • the hydrogen from the effluent stream may be used as a source of hydrogen to convert the lignin to lignin conversion products.
  • the water from the effluent stream may be recycled or reused as treatment water for pretreating the ligno-cellulosic biomass feedstock.
  • the conversion of the ligno- cellulosic biomass can begin with either pre-treated ligno-cellulosic biomass (20A or 20B) or untreated ligno-cellulosic biomass (10A or 10B).
  • the A stream is fed into an optional carbohydrate conversion process to convert the carbohydrates to useful products prior to converting the lignin.
  • the chosen feedstock enters the carbohydrate conversion reactor (100) via stream (110). Additional reactants, such as hydrogen are added into (120). If the ligno- cellulosic biomass is added as a slurry and a catalyst is used, the handling principles described creating the continuous process apply and reduce this process to practice as well.
  • the carbohydrate conversion products are passed from the carbohydrate conversion reactor (100) to carbohydrate conversion product recovery (200) via stream (210).
  • carbohydrate conversion products There can be two types of carbohydrate conversion products, one being gas exiting via (220).
  • This gas could be methane which can be converted to hydrogen by known technologies such as steam reforming.
  • the hydrogen would be used either to convert more carbohydrates or lignin by introducing the hydrogen into lignin conversion reactor (500) via stream (520). Should the embodiment produce ethylene glycol, that ethylene glycol would be transferred via stream (230) to a polyester manufacturing facility which would convert the ethylene glycol into polyester resin which is later converted to finished polyester articles such as preforms and polyester bottles.
  • the lignin from the carbohydrate conversion process enters the lignin slurry creation step (300) via stream (310).
  • the embodiment without the first carbohydrate conversion step is depicted by streams (20B) and (10B) respectively. As contemplated by the inventors, these could directly feed, and have been proven to be continuously converted when fed directly into the slurry creation step (300). Makeup water or other solvent is added via stream (320) with the optional vacuum being applied through stream (330).
  • step (300) can be skipped and the streams (10B) or (20B) fed directly into the slurry pump or slurry pumps (400) via stream (410).
  • the pumping system as described above increases the pressure of the slurry to greater than the reactor conversion pressure of the lignin conversion reactor (500).
  • the slurry pump will discharge the slurry comprised of lignin through an outlet valve (450) to the lignin conversion reactor (500) through stream (510).
  • Lignin conversion reactor (500) will contain the lignin slurry and at least the first catalyst. Hydrogen will enter the lignin conversion reactor (500) at pressure through stream (520). As a CSTR, the lignin conversion products are passed up through dip tube (610), with the catalyst settling back down into the lignin conversion reactor (500). Vessel (600) is the liquid solids separator, with the gas by-products exiting the separation vessel (600) via stream (710) and passing into the back pressure regulator (700) which controls the pressure of the whole system. After reducing the pressure, the gasses are passed through stream (720).
  • stream (720) will contain methane, a conversion product of the carbohydrates, thus the carbohydrate conversion process has been done in situ with the lignin conversion.
  • the methane can be further converted to hydrogen through steam reforming for example and re-used in the process, thus making the process at least partially self-sufficient in hydrogen.
  • the solids from the lignin conversion process are separated from the liquids in step (600) with the solid passing in stream (620) and the liquids passing to the BTX conversion step (800) via stream (810).
  • Stream (650) of Figure 3 shows the separation of water from the lignin conversion process. While the water will be present in the liquid phase, there may be some water vapor present in (720) as well. As depicted in Figure 1 , in this embodiment, at least a portion of the water is re-used to create or supplement the slurry comprised of lignin. As the lignin conversion process is a net water producer, some water will be purged in stream (620).
  • BTX benzene, toluene, xylenes
  • the experiments used a composition obtained from wheat straw as a starting raw material.
  • the raw material was subjected to a soaking treatment in water at a temperature of 155°C for 65 minutes then steam exploded at a temperature of 190°C for 4 minutes.
  • the steam exploded material and the liquids from soaking material were mixed together and subjected to enzymatic hydrolysis, fermentation to ethanol and distillation.
  • the mixture of liquid and solids after distillation was pressed at 15 bar and at a temperature of 80°C to obtain a dense and compact solid, having a dry matter content of 55% and characterized by the following composition on a dry matter basis.
  • Frozen lignin-rich composition was naturally unfrozen until reaching a temperature of 20°C.
  • De-ionized water was added to the lignin-rich composition to reach the final lignin-rich composition concentration in the slurry planned in each experiment.
  • the mixture was inserted into a blender (Waring Blender, model HGBSS6) and thoroughly mixed intermittently (e.g. pulsed on for 30 sec, left off for 30 sec) for 10 min to reach a homogeneous slurry.
  • the homogeneity of the slurry was evaluated by eye.
  • the slurry was inserted into a mix tank with constant agitation.
  • the mix tank was a stainless steel, dish bottom tank with a bottom discharge port connected to a Chandler Quizix QX dual syringe pump equipped with full port ball valves, connected to the lignin conversion reactor.
  • the pump discharge was connected to the reactor with tubing.
  • the lignin conversion reactor was a Parr 4575 reactor equipped with a dual 45° pitched turbine blade, cooling coil, separate gas and slurry feed ports and a discharge dip tube.
  • the reactor was charged with water (-220 mL) and catalyst (Johnson Matthey A-5000 sponge catalyst) according to the experimental conditions of each experiment and sealed.
  • the weight of catalyst introduced is indicated as the ratio between the weight of the catalyst and the weight of dry matter of the lignin-rich composition added to the lignin conversion reactor in one residence time.
  • Hydrogen at a temperature of 20°C was inserted into the lignin conversion reactor to reach a pressure of 48.3 bar.
  • the lignin conversion reactor was heated to a temperature corresponding to 90% of the reaction temperature and continuous flow of Hydrogen was started into the lignin conversion reactor.
  • the lignin conversion reactor was connected to a products receiver, maintained at 25 °C.
  • the pressure was measured by means of a pressure transducer (Ashcroft Type 62) connected to the lignin conversion reactor and controlled by means of a back-pressure regulator (Dresser Mity Mite 5000, model 91) placed downstream of the products receiver.
  • Temperature was increased to the reaction temperature and the flow of slurry comprised of lignin was introduced into the lignin conversion reactor.
  • the slurry flow rate was calculated for obtaining the residence time of the lignin feed in the reactor in each experiment at the operating conditions.
  • the untreated stillage in a glass sample container appeared as a dark brown homogeneous solution.
  • the liquid fraction Prior to being processed in the lignin conversion process the liquid fraction was dark brown to black, indicating a large amount of soluble contaminants.
  • the untreated stillage was 54,000 mg/L of COD.
  • the CODs of the water after processing in the lignin conversion process was 17,000 mg/L, a 69% reduction of CODs.
  • one embodiment of the process will produce an aqueous phase having a COD concentration preferably less than 50% of the COD concentration of the aqueous phase of the lignin feedstock of the lignin conversion process. With less than 40% being more preferred and less than 32% being most preferred.
  • the aqueous phase can be recycled or reused, with or without further COD removal or reduction of COD concentration, in the carbohydrate conversion step as the soaking water, the water of the steam explosion or other wash water or fermentation streams; or it can be re-used or recycled in the lignin conversion step as part of the slurry creation or make up water.
  • the re-use or recycle of just 10% of the aqueous phase has massive implications for the waste water treatment, which is a significant part of the expense of operating a carbohydrate conversion process, a lignin conversion process, or an integrated process.
  • the water from lignin-cellulosic feedstock was removed and visual and analytically evaluated prior to being processed in the lignin conversion process.
  • FIG. 3 This reuse of the water is depicted in Figure 3, where at least a portion of the water from the reaction is separated from the lignin conversion products and re-used in the process.
  • the water depicted as stream (650) could be used for the slurry at stream (320) or as part of the hydrolysis step at (120) of the carbohydrate conversion or used in the soaking or steam explosion steps of the pre-treatment. If not reused, the water is generally sent to waste water treatment for further purification and re-introduction into the environment.
  • composition of lignin-rich composition was determined according to the following standard procedures:
  • composition of liquid products were determined by means of Agilent 7890 Gas chromatogram and Agilent 5975C Mass Detector, according to the following procedure and parameters.
  • MSD transfer line (mass detector)
  • MS quad 150 °C Products and related percentage content relative to the weight of liquid products were identified by means of NIST 2008 peak identification software. Only products corresponding to an area greater than 1 % of the whole spectrum area are reported.
  • the filtered solids were dried and then ashed.
  • the burnt portion were considered unreacted lignin.
  • the ash portion was considered nickel catalyst.
  • the non-condensed gases were identified by gas chromatography.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne un procédé de conversion d'une charge de lignine convertie en produit de lignine converti constitué de composés aromatiques, le procédé comprenant l'étape d'exposition de la charge de lignine convertie à au moins un catalyseur en présence d'une pluralité de molécules donneurs d'hydrogène à une température de réaction de 190 à 350°C pendant un temps de réaction d'au moins 30 minutes. La charge de lignine convertie comprend une huile phénolique, et au moins une partie de la pluralité des molécules donneurs d'hydrogène est donnée lors de l'exposition de la charge de lignine convertie et de la pluralité de molécules donneurs d'hydrogène audit catalyseur à la température de réaction pendant le temps de réaction.
EP13759462.8A 2012-10-28 2013-08-27 Procédé continu de conversion de lignine en composés utiles Withdrawn EP2912146A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13759462.8A EP2912146A1 (fr) 2012-10-28 2013-08-27 Procédé continu de conversion de lignine en composés utiles

Applications Claiming Priority (22)

Application Number Priority Date Filing Date Title
US201261719486P 2012-10-28 2012-10-28
US201361751919P 2013-01-13 2013-01-13
US201361764611P 2013-02-14 2013-02-14
US201361765402P 2013-02-15 2013-02-15
PCT/EP2013/053631 WO2013124461A2 (fr) 2012-02-24 2013-02-22 Procédé continu destiné à la conversion de lignine en composés utiles
PCT/EP2013/053628 WO2013124458A2 (fr) 2012-02-24 2013-02-22 Procédé continu de conversion de lignine en composés utiles
PCT/EP2013/053629 WO2013124459A2 (fr) 2012-02-24 2013-02-22 Procédé continu de conversion de lignine en composés utiles
PCT/EP2013/053625 WO2013124456A2 (fr) 2012-02-24 2013-02-22 Procédé continu destiné à la conversion de lignine en composés utiles
PCT/US2013/027393 WO2013142006A2 (fr) 2012-02-24 2013-02-22 Procédé en continu de conversion de la lignine en composés utiles
PCT/EP2013/053630 WO2013124460A2 (fr) 2012-02-24 2013-02-22 Procédé continu de conversion de lignine en composés utiles
PCT/EP2013/053626 WO2013124457A2 (fr) 2012-02-24 2013-02-22 Procédé continu de conversion de lignine en composés utiles
US13/775,230 US9139501B2 (en) 2012-02-24 2013-02-24 Continuous process for conversion of lignin to useful compounds
US13/775,239 US9732021B2 (en) 2012-02-24 2013-02-24 Continuous process for conversion of lignin to useful compounds
US13/775,229 US20130225853A1 (en) 2012-02-24 2013-02-24 Continuous process for conversion of lignin to useful compounds
US13/775,238 US9035117B2 (en) 2012-02-24 2013-02-24 Continuous process for conversion of lignin to useful compounds
US13/775,241 US20130225856A1 (en) 2012-02-24 2013-02-24 Continuous process for conversion of lignin to useful compounds
US13/775,242 US9340476B2 (en) 2012-02-24 2013-02-24 Continuous process for conversion of lignin to useful compounds
US13/775,240 US9162951B2 (en) 2012-02-24 2013-02-24 Continuous process for conversion of lignin to useful compounds
US201361837262P 2013-06-20 2013-06-20
US201361866734P 2013-08-16 2013-08-16
PCT/EP2013/067734 WO2014063852A1 (fr) 2012-10-28 2013-08-27 Procédé continu de conversion de lignine en composés utiles
EP13759462.8A EP2912146A1 (fr) 2012-10-28 2013-08-27 Procédé continu de conversion de lignine en composés utiles

Publications (1)

Publication Number Publication Date
EP2912146A1 true EP2912146A1 (fr) 2015-09-02

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EP13759462.8A Withdrawn EP2912146A1 (fr) 2012-10-28 2013-08-27 Procédé continu de conversion de lignine en composés utiles

Country Status (1)

Country Link
EP (1) EP2912146A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190111264A (ko) 2018-03-22 2019-10-02 한국과학기술연구원 바이오매스를 이용한 고리형 및/또는 방향족 화합물의 제조방법

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2014063852A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190111264A (ko) 2018-03-22 2019-10-02 한국과학기술연구원 바이오매스를 이용한 고리형 및/또는 방향족 화합물의 제조방법

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