JP2016508177A - A continuous process for the conversion of lignin into useful compounds. - Google Patents

Abstract

This specification discloses a method for converting a lignin biomass feed stream into a converted lignin stream comprising aromatic compounds. The process includes combining lignin and at least one solvent and at least one catalyst in a reaction vessel. Preferably, the ratio of moles of catalyst to moles of lignin is in the range between 4: 1 and 15: 1. The lignin biomass feed stream is then deoxygenated to a converted lignin stream at a deoxygenation temperature and deoxygenation pressure during the deoxygenation time.

Description

Priority and cross-reference This application is filed in US Provisional Patent Application No. 61 / 751,919 filed on January 13, 2013, US Provisional Patent Application No. 61/754, filed on February 14, 2013. No. 611, US Provisional Patent Application No. 61 / 765,402 filed on Feb. 15, 2013, International Application No. PCT / US2013 / 027393, Feb. 26, 2013, filed Feb. 22, 2013 International application PCT / EP2013 / 053625 filed on February 26, 2013 International application PCT / EP2013 / 053626 filed on February 26, 2013, International application PCT / EP2013 / 053628 filed on February 26, 2013 International application PCT / EP2013 / 053629, filed February 26, 2013, filed February 26, 2013 International Application PCT / EP2013 / 053630, International Application PCT / EP2013 / 053631 filed on February 26, 2013, International Application PCT / EP2013 / 067734 filed on October 27, 2013, 2013 US Patent Application No. 13 / 775,229 filed February 24, US Patent Application No. 13 / 775,230 filed February 24, 2013, filed February 24, 2013 U.S. Patent Application No. 13 / 775,238, U.S. Patent Application No. 13 / 775,239 filed on Feb. 24, 2013, U.S. Patent Application No. 13/775, filed on Feb. 24, 2013 240, U.S. Patent Application No. 13 / 775,241, filed February 24, 2013, U.S. Patent, filed February 24, 2013 Application No. 13 / 775,242, US Provisional Patent Application No. 61 / 837,262, filed June 20, 2013, US Provisional Patent Application No. 61/866, filed August 16, 2013 734, and US Provisional Patent Application No. 61 / 892,617, filed Oct. 18, 2013, each of which is incorporated herein by reference. .

  The conversion of lignin in a batch process using hydrogen and a catalyst is known. For example, Non-Patent Document 1 discloses exposing air-dried poplar to hydrogen and Raney nickel in a batch autoclave at 340 ° C. to 350 ° C. for 1 or 2 hours to produce an “oil product”.

  However, according to (Non-Patent Document 1), "The use of Raney nickel is currently stopped by selecting nickel from nickel salts ...".

  The use of catalysts to recover lignin is also known. (Non-Patent Document 2) is a comprehensive review of catalytic attempts to convert lignin.

  While many theoretical continuous methods have been proposed, the inventors are not aware of any disclosure to the extent that they can be implemented beyond the theoretical basis. For example, conversion of solid lignin presents an important handling problem as shown in (Non-patent Document 3).

  “High pressure supply systems for biomass slurries have been recognized as a process development issue since the Arab oil embargo in 1973, at least as long as modern biomass conversion systems are under development. The slurry pumping system is outlined, with the vast majority including ball check valves, and our conclusion is that the high pressure supply leaves challenges for small scale production, The high pressure feed of the slurry should be more easily achieved at higher flow rates and the biomass fiber is expected not to bridge and plug the orifices and valves.

  Therefore, there is a need to provide a pumping and charging scheme for the slurry.

  Examples of this are (Patent Literature 1), (Patent Literature 2), (Patent Literature 3), (Patent Literature 4), (Patent Literature 5), (Patent Literature 6), (Patent Literature 7), and (Patent Literature 7). It exists in a series of applications 8). These applications by common inventors propose a continuous process based solely on batch autoclave results and demonstrate the high catalyst selectivity of ethylene glycol. However, high ethylene glycol yields depend on the purity of the cellulose raw material that is intuitively cleaved to 3 units of ethylene glycol. Of the experiments listed, the experiment that uses the feedstock closest to the biomass feedstock found in industrial or natural environments is bleached pulp. However, the bleached pulp produced only a 37% yield. If hemicellulose is used (xylose), the results are expected to be shifted to propylene glycol far away from ethylene glycol. While a continuous process is theoretically described, this application cannot disclose a continuous process to the extent practicable. For example, the disclosure states: “Continuous process materials must be able to be transported from a low pressure source into the reaction zone and the product must be transportable from the reaction zone to the product recovery zone. Depending on the mode of operation, residual solids, if present, must be able to be removed from the reaction zone. Although this discloses intuitively obvious requirements for operating a continuous process, this description cannot teach how one of ordinary skill in the art will achieve those requirements. This essential problem is not discussed or solved in this application. In fact, during the discussion of FIG. 2 of this publication, temperature and pressure conditions are discussed without any disclosure regarding how the slurry can be raised to a listed pressure of 1800 psig, or even 200 psig. In view of the transportation challenges that exist as of 2006 since the 1973 oil embargo, disclosure that teaches those skilled in the art that material transportation is important can hardly be considered feasible.

  These series of applications also disclose holding water in the liquid phase in the reaction zone. This occurs due to tightness in the batch autoclave. However, this cannot disclose how to do this in a continuous process or even whether it can be done.

  In the above applications and publications, dissolution of lignin has been proposed to avoid the pumping and charging problems described but not solved. (Patent Document 9) relies on the dissolution of lignin such that the material can be charged as a liquid, fully utilizing a check valve and high pressure liquid charging system. In fact, according to (Patent Document 9), “the only limitation is that the lignin supplied to the hydrocracking reaction is sufficiently dissolved in the solvent at the supply temperature”.

  Conversion of the product of the converted lignin feed stream to basic aromatics has long been industrially desired. Attempts have been made to convert the product of the converted lignin feed stream under low harsh conditions (<190 ° C.). However, these conditions have proved useless in obtaining aromatic compound selectivity in a few, but not all, models.

  Therefore, there is a need for a disclosure that is adequate to implement how to continuously convert lignin, including the conditions essential to handling, charging, and the process to be performed. There is also a need to provide a process that can produce a substantial proportion of aromatic compounds from a lignin derived feed stream. These conditions and steps represent both novelty and inventiveness and are considered the first to be experimentally feasible.

US Patent Application Publication No. 2011/0312051 US Patent Application Publication No. 2011/0312487 US Patent Application Publication No. 2011/0312488 US Patent Application Publication No. 2011/0313212 US Patent Application Publication No. 2011/0313210 US Patent Application Publication No. 2011/0313209 US Patent Application Publication No. 2011/0313208 Specification US Patent Application Publication No. 2011/0312050 International Publication No. 2011/117705

Boocock, D.C. G. B et al, “The Production of Synthetic Organic Liquids From Wood Using a Modified Nickel Catalyst” Zakzeski, Pieter C, et al; “The Catalytic Valuation of Lignin for the Production of Renewable Chemicals”, 2010. PNNL-16079, September 2006

  Disclosed herein is a method for conversion of a converted lignin biomass feed stream to a converted lignin stream. The method disclosed herein is to combine a first catalyst with a lignin biomass feed stream comprising lignin and at least a first solvent in a reaction vessel, the number of moles of the first catalyst and the mole of lignin. Deoxygenated and converted lignin stream from the lignin biomass feed stream at a deoxygenation temperature and deoxygenation pressure during the process wherein the ratio of the number is between 4: 1 and 15: 1 and during the time of deoxygenation The process of making.

  In one embodiment of the method described herein, the ratio of moles of first catalyst to moles of lignin ranges between 4: 1 and 12: 1. In a further embodiment, the ratio of moles of first catalyst to moles of lignin ranges between 4: 1 and 10: 1. In still further embodiments, the ratio of the number of moles of first catalyst to the number of moles of lignin ranges between 4: 1 and 9: 1. In yet another embodiment, the ratio of moles of the first catalyst to moles of lignin ranges between 5: 1 and 9: 1.

  In one embodiment of the method described herein, the deoxygenation temperature ranges between 205 ° C and 325 ° C. In a further embodiment, the deoxygenation temperature ranges between 215 ° C and 300 ° C. In still further embodiments, the deoxygenation temperature ranges between 225 ° C and 280 ° C.

  In one embodiment of the method described herein, the first catalyst comprises a metal catalyst, wherein the metal is selected from the group consisting of nickel, palladium, platinum, ruthenium, rhodium, molybdenum, cobalt, and iron. .

  In one embodiment of the method described herein, the deoxygenation pressure ranges between 60 bar and 100 bar. In a further embodiment, the deoxygenation pressure ranges between 70 bar and 100 bar. In yet another embodiment, the deoxygenation pressure ranges between 75 bar and 95 bar.

  In one embodiment, the deoxygenation time ranges between 5 minutes and 2 hours. In a further embodiment, the deoxygenation time ranges between 10 minutes and 1.5 hours. In yet another embodiment, the deoxygenation time ranges between 15 minutes and 1 hour.

It is a schematic description of the unit operation of the fully integrated process which continuously converts a lignocellulosic biomass raw material into a polyester bottle. Fig. 4 shows a further embodiment of the process. 7 illustrates one embodiment using at least a portion of water from a lignin conversion process that is reused in an integrated facility pretreatment or slurry creation step. 1 illustrates one embodiment of a continuous stirred tank reactor for a lignin conversion process. Figure 6 shows the effect of mixing and vacuum on final dispersion concentration versus time. FIG. 2 shows a schematic diagram of a piston pump and valves used to charge a slurry containing lignin into a lignin conversion reactor. FIG. 2 shows a schematic diagram of a piston pump and valves used to charge a slurry containing lignin into a lignin conversion reactor. The schematic diagram of a bubble column is shown. Figure 2 shows the ability of a bubble column to convert a slurry containing lignin into a lignin conversion product equivalent to that achieved from a continuous stirred tank reactor.

  This specification is a feasible disclosure and actual implementation of a high yield continuous lignin conversion process, especially from biomass feedstock. Approximately 80% of the available lignin in the feed is recovered as a usable product.

  Although not clear from the numbers, the disclosed process is a very high yield conversion process. Approximately, 1 kg of biomass feedstock used contained 50% lignin, 41% carbohydrates and 9% ash by weight of dry feed.

The demonstrated high lignin recovery for a process based on 1 kg of raw material is as follows:
50% dry weight of the raw material is not lignin, it is broken down or not used in the case of ash because it is not readily available. Of the remaining lignin, 35-40% by weight of the lignin is oxygen, which is removed (deoxygenated) from the process. Thus, 50% of the raw material is lignin, while 40% of its weight is unusable lignin (oxygen), leaving only 30% of the total weight of the raw material as the theoretical recovered amount of lignin. The following experiments recovered up to 24-26% by weight of the feed, or about 80% of the theoretically available lignin was converted to usable oil.

  As described in the Background section, many continuous lignin and biomass reactors have been proposed that have been developed based on lignin conversion data from batch autoclaves. These prior disclosures attempt to teach and enable continuous processes. However, these are not disclosures to the extent that they can be implemented and are generally inoperable as these methods cannot address the challenges of continuous processes.

  As an example, the continuous process produced very small amounts of long chain aliphatic hydrocarbons, while the equivalent batch process produced significant amounts of long chain aliphatic hydrocarbons. The continuous process is thought to have broken down carbohydrates into very low molecular weight, low boiling molecules such as methane and carbon dioxide and removed them through the effluent gas. In batch processes, these compounds are believed to be retained in the reactor and further converted to long chain aliphatic hydrocarbons (greater than 12 carbons). Thus, in the continuous process of the present disclosure, the amount of aliphatic carbon having more than 11 carbons expressed as a percentage of the total weight of the conversion product is less than 10 wt%, more preferably less than 8 wt%. Less than 5% by weight is even more preferred, and less than 2.5% by weight is most preferred.

  The above problem is only one of many that the present inventors face when using an industrial lignocellulosic raw material and creating a continuous process that does not use a model compound. Due to these challenges, claims cannot be made to the extent that a theoretical continuous method can be predicted and implemented based on batch data or model compounds.

  This specification not only fully enables those skilled in the art to operate a continuous process for converting lignin to liquid oil, but the specification also describes the subsequent use of oil to make polyester bottles or containers. The use is also disclosed.

Lignin The claimed method utilizes a feed or raw material containing lignin. It can also utilize a raw material consisting of lignin, or a raw material consisting essentially of lignin, or a raw material containing at least 95% by weight of lignin.

  Lignin does not have a single chemical structure. In fact, according to Kirk Othmer Encyclopedia, the exact chemical structure of lignin is unknown because it occurs in wood and is difficult to extract from wood without changing its structure, so the exact structure Cannot be known. While there are many variants of lignin, the term lignin as used herein refers to any polymer containing p-hydroxyphenyl units, syringyl units, and guaiacyl units.

  While pure lignin, such as organosolv, acetosorb lignin, can be used, extraction of lignin from its natural source is expensive using organic solvents and is associated with environmental problems. The robustness of the claimed method is established by the fact that when lignin is found in a lignin-cellulosic biomass feedstock, it is experimentally demonstrated on a continuous basis that the method converts lignin.

Lignin cellulosic biomass feedstock The lignin to be converted in the present invention can be present as a feed or feedstock of natural lignocellulosic biomass comprising at least one carbohydrate and lignin. Depending on how the natural lignocellulosic biomass is treated, another embodiment of the feedstock may have the following composition and specific decomposition temperature and surface area:

Since the feed can use naturally occurring lignocellulosic biomass, the stream has a relatively young carbon material. The following excerpt from ASTM D6866-04 describes modern carbon, which is found in bio-based hydrocarbons, as opposed to oil-derived hydrocarbons derived from biomass thousands of years ago. It is what “A direct indicator of the relative contribution of fossil carbon and carbon from the living biosphere can be expressed as the rate (or percentage) of modern carbon, the symbol f _C. Derived from f _M through the use of an observed input function of medium ¹⁴ C and represents the combined effect of fossil dilution (minority) and increase (mass) from nuclear experiments with ¹⁴ C. f _C and f _M The relationship between is necessarily a function of time, and by 1985 when particulate sampling was considered in the cited document [ASTM D6866-04, the teaching of which is incorporated by reference in its entirety], the f _M ratio is , Decreased to about 1.2. "

Fossil carbon is essentially free of radioactive carbon because its age is much older than the ¹⁴ C half-life of 5730 years. Modern carbon is clearly 0.95 times the specific activity of SRM4990b (prototype oxalate radiocarbon standard) normalized to δ ¹³ C = −19%. Functionally, the proportion of modern carbon = (1 / 0.95), and unit 1 is defined as the concentration of ¹⁴ C at the same time as the tree in [Era] 1950 (ie before atmospheric nuclear testing). , 0.95 is used for correction after the introduction of ¹⁴ C into the atmosphere by the 1950 nuclear bomb. As described in the Analytical and Test Method Interpretation section, 100% of ¹⁴ C represents a completely modern carbon source, for example a product derived from the method. Thus, the ¹⁴ C percent of the product stream from this method is at least 75%, more preferably 85%, more preferably 95%, even more preferably at least 99%, and most preferably at least 100% (test method is Note that the ¹⁴ C percent can be slightly higher than 100% for reasons described in the method). These proportions can also be equal to the amount of modern carbon as well.

  Thus, the amount of modern carbon relative to the total amount of carbon is preferably at least 75%, more preferably 85%, even more preferably 95%, even more preferably at least 99%, and most preferably at least 100%. Correspondingly, each carbon-containing compound in a reactor comprising a plurality of carbon-containing conversion products is preferably at least 75%, more preferably 85%, even more preferably 95%, and at least 99% Even more preferred, at least 100% has the most preferred amount of modern carbon relative to the total amount of carbon.

  In general, natural or naturally occurring lignocellulosic biomass can be one feedstock for the process. The lignocellulosic material can be described as follows.

  Apart from starch, the three main components in plant biomass are cellulose, hemicellulose and lignin, which are commonly referred to by the generic name lignocellulose. Collectively polysaccharide-containing biomass includes both starch and lignocellulosic biomass. Thus, some types of raw materials can be plant biomass, polysaccharide-containing biomass, and lignocellulosic biomass.

  The polysaccharide-containing biomass according to the invention includes, for example, any material containing starch and polymeric sugars in the form of purified starch, cellulose and hemicellulose.

  Related types of naturally occurring biomass to guide the claimed invention include starch-containing grains, refined starch; corn stover, bagasse, straw, such as rice, wheat, rye, oats, barley, oilseed rape, sorghum Softwood such as Pinus sylvestris, Pinus radiate; hardwood such as Salix spp., Eucalyptus spp .; tuber such as beet, Potatoes; for example, crops selected from the group consisting of cereals from rice, wheat, rye, oats, barley, rape, sorghum and corn; waste paper, fiber division from biogas treatment, compost, residue from oil palm treatment , It may include biomass derived from, such as the city solid waste. Although the experiment is limited to a few examples of the lists listed above, the present invention is considered applicable to all. This is because the characterization is primarily on the inherent characteristics and surface area of lignin.

  The lignocellulosic biomass feedstock used to derive the present composition is preferably from a family commonly referred to as grasses. Appropriate names are the families known as Poaceae or Gramineae in the monocotyledonous family of flowering plants (Liliopsida) (monocotyledonous plants). Plants of this family are usually referred to as Enomoto or to authenticate them to distinguish them from other Gramineae plants. Bamboo is also included. There are approximately 600 genera and approximately 9,000-10,000 or more species (World Index Specials, Kew Index).

  Poaceae includes staple grains and cereal crops, lawns and forage grasses, and bamboos grown around the world. Poaceae generally have hollow stems called cocoons that are plugged (solid) at intervals called nodes, where the nodes are points along the heel where the leaves form. Enomoto's leaves are usually parallel, anti-vibration (in one plane) or rarely spiral. Each leaf is differentiated between a lower leaf sheath that has a stem at a certain distance and a leaf blade that is usually full-length. Many Enomoto leaf blades are hardened by silica phytosilicates, which help keep herbivores away. In some samples (eg, sword glass), this makes the edges of the sample leaf blade sharp enough to cut the human skin. A membranous appendage or tuft of hair, called the leaf tongue, is present at the junction between the leaf sheath and leaf blades and prevents water or insects from entering the leaf sheath.

  Enomoto's leaf blades grow at the base of the leaf blades and do not grow from the elongated shoot apex. This low growth point evolves in response to herbivores, allowing for regular grazing or cutting of plants without undue damage to the plant.

  Poaceae flowers are characteristically placed in spikelets, and each spikelet has one or more florets (spikelets are further broadly divided into conical or spikes). . A spikelet consists of two (or possibly less) leaflets at the base called bales followed by one or more florets. A floret consists of a flower surrounded by two cocoon leaves, called the outer bud (outside) and the inner bud (inner). The flowers are usually hermaphroditic (except for hermaphroditic corn), and pollination is almost always airborne. The flower coat is grouped into two bud scales called scale coats that expand and contract to expand the outer and inner wings; these are generally interpreted as deformed pieces.

  Poaceae fruits are fruits that have a seed coat fused to the peel and therefore cannot be separated therefrom (as in corn kernels).

  Enomoto has three general classes of growth habits: bundle type (also called colony), toothpick type, and rhizome.

  Enomoto's achievements exist partly in their morphology and growth process, and partly in their physiological diversity. Most of the books fall into two physiological groups that use the C3 and C4 photosynthetic pathways for carbon fixation. C4 variants have photosynthetic pathways linked to specialized leaf crants structures that make them particularly suitable for high temperature climates and low carbon dioxide atmospheres.

  C3 transcripts are referred to as “cold season transcripts” while C4 plants are considered “warm season transcripts”. Enomoto can be either a first year or a perennial. Examples of annual cold season are wheat, rye, annual bluegrass (annual meadowgrass, Poa annua and oats). Examples of perennial cold seasons are orchardgrass (Dactylis glomerata), oxenogusa (Festaca spp), Kentucky bluegrass and Lolium perenne. Examples of annual warming seasons are corn, Sudangrass and pearl millet. Examples of perennial warm periods are big blue stem, Indian glass, Bermuda glass and switch glass.

  One classification of the family is Twelve subfamily: These are: 1) Anomocroa subfamily, which is a small strain of broadleaf genus including two genera (Anomochlora, Streptocheta) 2) Three genera, including, for example, Pharoideae, a small lineage of genus including Pharus and Leptaspis; 3) Small, including the African genus Puelia Lines Puelioidee; 4) Strawberry subfamily including wheat, barley, oats, brongras and leadgrass (Calamagrostis); 5 Bambousideae containing bamboo; 6) Rice, and Ehrhartoideae containing wild rice; 7) Arundinoideae containing pear and reed 8) Panicoideae The subfamily of 11 genera that may also be included in the genus, Cenotecoideae; 9) Chloridoidee, for example, Rabgrass (Eragrostis), about 350 species, Tef), drop seed (Sporobolus, about 160 species), millet (Eleusine coracana (L.) Gaertn.), And Moury grass (Muhlenb) ergia), about 175 species); 10) Panicoideae, for example, panic glass, corn, sorghum, sugar cane, most millet, fonio and blue stemgrass; 11) Micrairoideae) and 12) Danthoniodiae, for example, Pampasgrass; about 500 species of strawberry genus (Poa) are native to the temperate regions of both hemispheres.

  Agricultural samples that grow for edible seeds are called cereals. Three common cereals are rice, wheat and corn (corn). Of all the crops, 70% are Japanese.

  Sugarcane is a major source of sugar production. Enomoto is used for construction. Scaffolds made from bamboo can withstand winds of typhoon forces that destroy steel scaffolds. The larger bamboo and dungeon (Arundo donax) has a sturdy firewood that can be used in the same way as timber, and the roots of Enomoto stabilize the turf of the turf house. Arundo is used to make reeds for woodwind instruments, and bamboo is used for many tools.

  Another naturally occurring lignocellulosic biomass feedstock may be from woody plants or wood. Woody plants are plants that use wood as their structural organization. These are typically perennials whose stems and larger roots are reinforced by wood produced adjacent to the vascular tissue. The main stems, larger branches, and roots of these plants are usually covered by a thickened bark layer. Woody plants are usually either trees, shrubs or vines. Wood is a structural cell adaptation that allows woody plants to grow from the ground stem year after year, thus making some woody plants the largest and longest.

  These plants require a vascular system to move water and nutrients from the roots to the leaves (xylem) and sugar from the leaves to the rest of the plant (phloem). There are two types of xylem: a primary xylem formed during primary growth from the pre-forming layer and a secondary xylem formed during secondary growth from the vascularization layer.

  What is usually called “wood” is the secondary xylem of such plants.

The two main groups that can find secondary xylem are:
1) Coniferous plant (Coniferae): There are about 600 species of coniferous plants. All species have secondary xylem that is relatively uniform in structure across this group. Many coniferous plants become tall trees: the secondary xylem of such trees is marketed as softwood.
2) Angiosperms (Angiospermae): There are approximately 250,000 to 400,000 angiosperms. Within this group, secondary xylem has not been found in monocotyledonous plants (eg, Poaceae). Many non-monocotyledonous angiosperms become trees and their secondary xylem is marketed as hardwood.

  The term softwood useful in the present method is used to describe wood from trees belonging to gymnosperms. A gymnosperm is a plant having bare seeds that are not encased in the ovary. These seed “fruits” are considered more primitive than hardwood. Softwood trees are usually evergreen, carry cones, and have bud scales like needles or leaves. These include coniferous plant species such as pine, spruce, fir and cedar. Wood hardness varies depending on the cone type.

  The term hardwood useful in the present method is used to describe wood from trees belonging to the Angiospermaceae family. Angiosperms are plants with ovules that are wrapped for protection in the ovary. At fertilization, these ovules develop into seeds. Hardwood trees are usually broad-leaved; in temperate and cold latitudes they are mostly deciduous, but are almost evergreen in the tropics and subtropics. These leaves can be single leaves (single leaf blades) or they can be compound leaves with leaflets attached to the petiole. Although the shape can vary, all hardwood leaves have a clear network of fine veins. Hardwood plants include, for example, aspen, birch, cherry, maple, oak and teak.

  Accordingly, preferred naturally occurring lignocellulosic biomass can be selected from the group consisting of cocoons and wood. Another preferred naturally occurring lignocellulosic biomass can be selected from the group consisting of cones, angiosperms and plants belonging to the family Poaceae. Another preferred naturally occurring lignocellulosic biomass may be a biomass having at least 10% by weight of the dry matter as cellulose, or more preferably at least 5% by weight of the dry matter as cellulose.

  The carbohydrates making up the present invention are selected from the group of carbohydrates based on glucose, xylose, and mannose monomers and mixtures thereof.

  The raw material containing lignin can be naturally occurring lignocellulosic biomass ground into small particles, or further processed. One process for producing a raw material containing lignin includes the following steps.

Preferred pretreatment It has been theorized that the pretreatment of the raw material is a solution to the difficulty of processing insoluble solid raw materials containing lignin or polysaccharides in a pressurized environment. According to US 2011/0312051, sizing, grinding, drying, high temperature catalyst treatment and combinations thereof are suitable pretreatments of raw materials to facilitate continuous transportation of raw materials. US 2011/0312051 does not present any experimental evidence, while weak acid hydrolysis of polysaccharides, catalytic hydrogenation of polysaccharides, or enzymatic hydrolysis of polysaccharides creates transportable feedstocks It is claimed that everything is suitable for the purpose. US Patent Application Publication No. 2011/0312051 describes a lower molecular weight than hydrothermal treatment, steam treatment, heat treatment, chemical treatment, biological treatment, or catalytic treatment is easily transported compared to untreated. It is also claimed that it can result in the following polysaccharides and depolymerized lignin. While this can aid in transportation, there is no disclosure or resolution of how to pressurize the solid-liquid slurry obtained from the pretreatment. In fact, as the inventors understood, the conventional wisdom and conventional system used to pressurize slurries did not work when pretreated lignocellulosic biomass feedstock was used.

  In integrated second generation industrial operations, pretreatment makes the structure of lignocellulosic inclusions accessible by catalysts such as enzymes, while at the same time harmful inhibitory by-products such as acetic acid, furfural and hydroxymethylfurfural. Often used to ensure that the concentration remains substantially low. There are several strategies for achieving increased accessibility, many of which can be invented in the future.

The current pretreatment policy is to subject the lignocellulosic biomass material to a temperature of 110-250 ° C. for 1-60 minutes, for example:
Multistage dilute acid hydrolysis to remove dissolved material before hot water extraction inhibitor is formed Diluted acid hydrolyzed alkaline wet oxidative steam explosion in relatively low harsh conditions.

  A preferred pretreatment of the naturally occurring lignocellulosic biomass comprises immersing the naturally occurring lignocellulosic biomass feedstock and then steam blasting at least a portion of the soaked naturally occurring lignocellulosic biomass feedstock.

  Immersion is carried out in either a substance, for example, water vapor in the form of evaporation, or water in liquid form, or in liquid and water vapor to produce a product. The product is a submerged biomass containing a first liquid, which is usually a liquid or an evaporating form, or some mixture of water.

  This soaking can be done by any number of techniques that expose the material to water, which can be water vapor or a liquid or a mixture of water vapor and water, or more generally at high temperature and pressure. The temperature should be 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 can be long, for example, 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 exposure time is preferably very short, from 1 minute to 6 The time ranges from 1 minute to 4 hours, 1 minute to 3 hours, 1 minute to 2.5 hours, more preferably 5 minutes to 1.5 hours, 5 minutes to 1 hour, and 15 minutes to 1 hour.

  If steam is used, it is preferably saturated but can be overheated. The dipping step can be batch or continuous with or without agitation. Low temperature immersion can be used before high temperature immersion. The temperature of the low temperature immersion is in the range of 25 to 90 ° C. The time can be long, but can be, for example, 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 exposure time is preferably very short, from 1 minute The range is 6 hours, 1 minute to 4 hours, 1 minute to 3 hours, 1 minute to 2.5 hours, more preferably 5 minutes to 1.5 hours, 5 minutes to 1 hour, 15 minutes to 1 hour.

Any dipping step may involve the addition of other compounds, such as H ₂ SO ₄ , NH ₃ , to achieve higher performance after the process. However, it is preferred that no acid, base or halogen is used anywhere in the process or pretreatment. The feed is preferably devoid of added sulfur, halogens and nitrogen. When present, the amount of sulfur in the composition is in the range of 0 to 1% by dry weight of the total composition. Further, when present, the amount of total halogen is in the range of 0 to 1 dry weight percent of the total composition. By making the raw material free of halogen, there is no halogen in the lignin conversion product.

  The product containing the first liquid is then run through a separation step to separate the first liquid from the soaked biomass. The liquid does not completely separate so that at least a portion of the liquid, preferably as much liquid as possible, is separated in an economical time frame. The liquid from this separation step is known as the first liquid stream containing the first liquid. The first liquid is a liquid used in dipping, generally water and a soluble species of raw material. These water-soluble species are glucan, xylan, galactan, arabinan, glucolygomer, xylo-oligomer, galacto-oligomer and arabino-oligomer. The solid biomass is referred to as the first solid stream. That is because it contains most if not all of the solids.

  The separation of the liquid can again be carried out by known techniques and suitable ones that can be invented in the future. One preferred device is a press. This is because the press produces a liquid under high pressure.

The first solid stream is then steam blasted to produce a steam blast stream comprising the solid and the second liquid. Steam explosion is a well-known technique in the biomass field and any system available today and in the future is considered suitable for this step. The severity of steam explosion is known in the literature as Ro, which is a function of time and temperature,
Ro = text [(T-100) /14.75]
The temperature T is expressed in degrees Celsius, and the time t is expressed in common units.

This equation is expressed as Log (Ro), that is,
Log (Ro) = Ln (t) + [(T−100) /14.75]
It is also expressed as

  Log (Ro) is preferably in the range of 2.8 to 5.3, 3 to 5.3, 3 to 5.0 and 3 to 4.3.

  The steam explosion stream can optionally be washed with at least water and there may be other additives used as well. It is envisaged that water is not considered absolutely essential since another liquid can be used in the future. At present, water is the preferred liquid and if water is used, it is considered a third liquid. The liquid effluent from the optional wash is a third liquid stream. This washing step is not considered essential and is optional.

  The cleaning blast flow is then treated to remove at least a portion of the liquid in the cleaning blast material. This separation step is also optional. The term removing at least a part makes it note that while removal of as much liquid as possible is desirable (press), it is unlikely that 100% removal is possible. In any case, 100% removal of water is not desired. This is because water is required for the subsequent hydrolysis reaction. The preferred process for this step is again a press, but other known and still uninvented techniques are considered suitable. The products separated from this process are solids in the second solid stream and liquids in the second liquid stream.

The steam explosion stream is then subjected to hydrolysis to create a hydrolysis stream. Optionally, at least a portion of the liquid of the first liquid stream is added to the steam explosion stream. Also, water is optionally added. Hydrolysis of the steam blast flow is achieved by contacting the steam blast flow with a catalyst. Enzymes and enzyme compositions are preferred catalysts. While laccase, an enzyme known to alter lignin, can be used, the composition preferably lacks at least one enzyme that converts lignin. The preferred hydrolysis of the steam explosion flow is
A) contacting the steam-cracked stream with at least a portion of the solvent (the solvent comprises a water-soluble hydrolyzed species; at least some of the water-soluble hydrolysed species are water-soluble resulting from hydrolysis of the steam-cracked stream The same as the hydrolyzed species);
B) maintaining the contact between the steam blast flow and the solvent at a temperature in the range of 20 ° C. to 200 ° C. for a time in the range of 5 minutes to 72 hours to create a hydrolyzed stream from the steam blast flow. including.

  The hydrolyzed stream comprises a carbohydrate monomer selected from the group consisting of glucose, xylose, and mannose.

  The hydrolyzed stream is subjected to fermentation to produce a fermented stream comprising the composition and water. Fermentation is performed by the addition of yeast or yeast composition to the hydrolyzed stream.

  Finally, hydrolysis and fermentation can be performed simultaneously according to the well-known technique of simultaneous saccharification and fermentation (SSF).

  Compositions derived from naturally occurring lignocellulosic biomass separate from the water in the fermentation stream. Separation of the liquid can be performed by known techniques and by suitable ones that can be invented in the future. One preferred device is a press.

  The composition differs from naturally occurring lignocellulosic biomass in that it has a large surface area as calculated according to the standard Brunauer, Emmett and Teller (BET) method.

BET surface area of the dry composition is at least 4m ² / g, in the range more preferably from 4 to 80 m ² / g, more preferably 50 m ² / gram to 4, even more preferably it is 25 m ² / gram to 4, 4 to 15 m ² / gram is even more preferred, and 4 to 12 m ² / gram is most preferred.

  The composition is further characterized by a peak generated during thermogravimetric analysis known as TGA.

  In thermogravimetric analysis, a plot of weight versus temperature and a plot of the first derivative of weight versus temperature are commonly used.

  If decomposition of a material or material component occurs within a specific temperature range, the plot of the first derivative of weight versus temperature represents the maximum value within the specific temperature range, also defined as the first derivative peak. . The value of the temperature corresponding to the first derivative peak is considered the decomposition temperature of the material or components of that material.

  A material is a composition of many components that decompose within different specific temperature ranges, and the plot of the first derivative of weight against temperature is the first derivative associated with the decomposition of each component within each specific temperature range. Represents a function peak. The temperature value corresponding to the first derivative peak is considered the decomposition temperature of each component of the material.

  In principle, the maximum value is located between the two minimum values. The temperature value corresponding to the minimum value is regarded as the initial decomposition temperature and the final decomposition temperature in the decomposition temperature range of the component corresponding to the first derivative peak whose decomposition temperature is included between the two minimum values. In this way, the derivative peak corresponds to the decomposition temperature range. The weight loss of a material within the range between the initial decomposition temperature and the final decomposition temperature is related to the decomposition of the material components and the first derivative peak.

  If the naturally occurring lignocellulosic biomass used to derive the lignin composition is a mixture of different species of cocoons or plants or other materials, the mixture of naturally occurring lignocellulosic biomass is It should be used for comparison with the derived material.

  The composition produced has the characteristic that the temperature corresponding to the maximum value of the first lignin degradation peak is less than the temperature corresponding to the maximum value of the first lignin degradation peak of the naturally occurring lignocellulosic biomass. . This difference is selected from the group consisting of at least 10 ° C, at least 15 ° C, at least 20 ° C, and at least 25 ° C above the temperature corresponding to the maximum value of the first lignin degradation peak of the naturally occurring lignocellulosic biomass. This is notable for the maximum value of the first lignin degradation peak which is lower by a certain value.

  This reduction in the maximum value of the first lignin decomposition temperature can be compared with the maximum value of the first lignin decomposition temperature after the pretreatment.

  Further, the absolute mass on a dry basis associated with the first lignin degradation peak of the claimed lignin composition is greater than the absolute mass on a dry basis of the second lignin degradation peak. For Arundo donax, the absolute mass of the first decomposition temperature of the naturally occurring lignocellulosic biomass is greater than the absolute mass of the second decomposition temperature of the naturally occurring lignocellulosic biomass, This is not the case with many lignocellulosic biomass, such as corn stover and wheat straw. However, after conversion, the lignin compositions derived from these biomass have a dry basis mass associated with the first lignin decomposition temperature that is greater than the dry basis mass associated with the second lignin decomposition temperature.

  By comparing the temperature associated with the maximum value of the first lignin degradation range to the temperature associated with the maximum value of the first lignin degradation range of the lignocellulosic biomass used to derive the feedstock, Further characteristics can be determined.

  The feedstock can also be further characterized by the relative amount of carbohydrates including glucan and xylan present on a dry basis. The composition may have an amount of total carbohydrate present in the composition in the range of 10 to 60%, more preferably 10 to 40%, and most preferably 5 to 35% of the dry weight of the composition. Of course, however, 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 carbohydrate and the weight percent of lignin is 100% of the dry weight of the raw material. %.

  Since the composition of the raw material containing lignin can vary depending on the starting material from which it is derived, the naturally-occurring lignocellulosic biomass from which the raw material is derived can be selected from the group consisting of cocoons and food crops.

Slurry Production The lignin can be charged to the lignin conversion reactor (500) as a solid slurried in liquid. In a preferred embodiment, the liquid can include water. In another embodiment, the liquid can include a hydrogen donor. The use of hydrogen donors is well known and is described in Wang, X, and Rinaldi, R .; "Exploiting H-Transfer reactions with RANEY (R) Ni for upgrade of phenolic and aromatic biorefinance federals, federal, low-severity." Sci. , 2012, 5, 8244.

  Lignin-containing slurries have several unique characteristics that make them difficult to create, maintain and handle, and in many instances, lignin-containing slurries have been found to behave differently than conventional slurries. .

  The solids content of the slurry containing lignin should be in the range of about 1 to 70% by weight, with a solids content of 5 to 35% by weight being more preferred. Conventionally, slurries are easier to maintain when the solids content is low. Surprisingly, slurries containing lignin are easier to maintain when the solids content is high (solids above 20% by weight).

  The particle size of the slurry containing lignin should be such that the number average size is in the range of less than 200 microns, preferably less than 150 microns and most preferably less than 100 microns. Particle size reduction is not necessary when the raw material containing lignin is steam exploded. However, particle size reduction may be necessary if the practitioner is starting from a naturally occurring lignin, such as a piece of wood.

  No surfactants or emulsifiers are required, but they can be used.

  There are several strategies for creating slurries containing lignin depending on the manufacturing location of the claimed method. When lignin conversion is co-located with pretreatment of lignocellulosic biomass (10) or carbohydrate conversion, lignin may already be present in slurry form, which is often referred to as stilage or stilage lignin, Has little or no water or lacks water-soluble sugars. When lignocellulosic biomass (10) is initially flowed through a pretreatment or carbohydrate conversion process, water soluble sugars are converted to species other than sugars. Water soluble sugars are washed away, extracted, or converted to species other than sugars by enzymes or catalysts, leaving a bottom liquor containing lignin and unconverted insoluble carbohydrates that are still mostly bound to lignin. These bottom liquids lack or substantially lack free water soluble sugars.

  In this iterative embodiment, the bottom liquid of a sugar or carbohydrate conversion process (eg, fermentation) (or what is often referred to as stilage or stilage lignin) is directly transferred to the next process where more carbohydrate can be further removed. Sink; or bottom liquid directly into the lignin conversion process described herein. In this way, water from a carbohydrate conversion process that must be processed through an otherwise expensive wastewater treatment plant is used as a slurry liquid to maintain or create a slurry containing lignin and supply it to the lignin conversion process. . The slag lignin, the slurry liquid removed from the lignin-containing carbohydrate conversion process, is then cleaned in situ with the hydrogen of the lignin conversion process while simultaneously converting the lignin. As described below, the slurry liquid resulting from the lignin conversion process has a total biochemical oxygen demand, also known as BOD, and / or a chemical oxygen demand, also known as COD, in the incoming slurry liquid from stilage lignin. Significantly lower than the amount of BOD and COD, thus reducing the amount of wastewater treatment and cost required prior to release of the slurry liquid to the environment. BOD and COD are chemically destroyed by the conditions of the lignin conversion process.

  In further refinement, at least a portion of the slurry liquid from the lignin conversion process can be used as make-up water or steam in the pretreatment process, thus significantly reducing the amount and cost of water treatment (FIG. 3). reference).

  This schematic is demonstrated in FIG. 3, where the lignocellulosic biomass (10) flows into the pretreatment process and flows the pretreated lignocellulosic biomass into a carbohydrate conversion process, in this case fermentation. In the carbohydrate conversion process, sugar is converted into one or more end products. It is preferred that the slurry liquid (620) from the lignin conversion process is introduced before or simultaneously with the steam explosion step of the pretreatment process.

  The bottom liquid, or stilage, containing lignin, slurry liquid, and possible carbohydrates is flowed to the slurry making step (300). If the stillage lignin is a sufficiently stable slurry and is at the desired concentration (eg, solid, buffer, pH), it can be processed without any further treatment, such as water dilution, water reduction, stirring, or vacuum. It can flow directly to the slurry pump (400).

  If adjustment is required, the slurry containing lignin is brought to optimal slurry conditions by adjusting the solids concentration under agitation and optionally under vacuum. Usually this is under high shear agitation of the slurry containing lignin.

  In some embodiments, the bottom liquid of the carbohydrate conversion process is delivered to a different location for lignin conversion. While it is possible to deliver already slurried stilage, the cost of delivery can be high due to the cost of delivering water. In this example, it is expected that the raw material containing lignin will be delivered as a solid, or that it will usually be dry with as much water as possible removed by filter pressing, drying, or both. Often, solid raw materials containing lignin are refrigerated or further frozen to prevent microbial growth during delivery or storage. The slurry liquid from the dehydration process is often sent to wastewater treatment where it is cleaned to remove BOD and COD and then released to the environment or reused as part of the pretreatment process. It is this external processing step that can be minimized or reduced by reusing or recycling at least a portion of the slurry liquid from the lignin conversion process.

  It has been directly observed that raw materials containing lignin are overly difficult to process and the particles are extremely difficult to separate. This is particularly the case when a raw material containing lignin is subjected to dehydration pressure as in a filter press and dehydrated. Visible light microscopy studies show that the raw material containing lignin has a tendril with vellus and heel that closely resembles Velcro®.

  As noted above, if the raw material after the carbohydrate conversion step is already a slurry, it may be possible to add the slurry directly to the process without further processing. However, in general this is not expected. After carbohydrate conversion, there is a high probability that there will be gas trapped in the stillage lignin to be removed.

  If the lignin conversion is not co-located with the pretreatment or fermentation of the lignocellulosic biomass (10), one strategy for creating a slurry containing lignin is to use a machine that can apply high shear forces and to apply high shear forces to the lignin. Is applied to an unslurried solid raw material. High shear force can be achieved by feeding a solid feed containing lignin through a blender. Preferred compounder embodiments include a twin screw co-rotating screw compounder, a twin screw reversing screw compounder, an extruder, a banbury, or another device known to impart mechanical force to material being processed through. It is.

  The amount of mechanical force required is related to the amount of energy required to make the solid raw material containing lignin readily dispersible. The higher the mechanical force applied to the raw material containing lignin, the easier the dispersion. The amount of mechanical force required can be determined iteratively by comparing the energy consumed with the energy required to disperse the resulting solids in the slurry liquid of the slurry. Techniques for varying the amount and type of mechanical force applied to a solid feedstock that includes lignin are equipment dependent and well known to those familiar with the particular machine used in the art.

  The slurry liquid can be added to a solid raw material containing lignin to produce a slurry containing lignin. It is preferable to add the slurry liquid to the solid raw material containing lignin after flowing out of the blender. In this regard, the solid raw material comprising lignin lacks free liquid, which means that it is preferred that the free liquid is contained in less than 5% of the weight of the composition and that there is no free liquid. In another embodiment, the slurry liquid can be added in a blender to a solid feed containing lignin. In a preferred embodiment, the slurry liquid includes water. In another embodiment, the slurry liquid can include a hydrogen donor. It should be noted that for the purposes of this specification, slurry liquids are also known as carrier liquids.

  The amount of energy consumed by the compounding machine required to produce a solid feedstock containing lignin that is easily dispersible in the slurry liquid and / or has a low viscosity when dispersed in the slurry liquid is the torque It can be determined by measuring. The amount of torque required to disperse the solid raw material containing lignin in the slurry liquid in the absence of the hydrolysis catalyst is less than the amount of torque required to disperse the solid raw material containing lignin before applying mechanical force. If it is less than 50% of the amount of torque required to be dispersed in the slurry liquid under the same conditions, it will be easily dispersed in the slurry liquid.

  The amount of torque is the total amount of energy applied to the solid-slurry liquid mixture to disperse the solid in the slurry liquid. The amount of torque can be determined by the area under the curve of the torque line applied at a given time t corresponding to the time at which the solid is considered dispersed in the slurry liquid. The solid is dispersed in the slurry liquid if the number average of the dry matter content percentage of the statistically effective number of aliquots of the slurry liquid is within 2.5% of the total dry matter content percentage in the slurry liquid. It is considered that

The viscosity of the slurry containing lignin measured at 25 ° C. and a shear rate of 10 s ⁻¹ of the mechanically dispersed solid feed containing lignin dispersed in the slurry liquid content is the same (eg, dry matter content ) When measured below, it should be less than the viscosity of the slurry of the solid feed containing lignin dispersed in the slurry liquid prior to mechanical processing.

  After producing the slurry containing lignin, the slurry containing lignin can be maintained by mechanical stirring.

  Another strategy to create a slurry containing lignin that does not place lignin conversion simultaneously with pretreatment or fermentation of lignocellulosic biomass (10) is to produce a slurry liquid, preferably a solid feed containing lignin in water, vacuum or large Exposure to pressures below atmospheric pressure, preferably less than 0.8 bar, more preferably less than 0.7 bar, even more preferably less than 0.4 bar, and most preferably less than 0.2 bar. The raw material containing lignin expands rapidly into small particles, dissociates and disperses. In this way, high shear mixing and / or high shear forces are avoided if higher concentrations are possible. It is preferred to have at least some mechanical agitation that occurs simultaneously with the vacuum step to disperse the particles more rapidly. The slurry creation experiment section and FIG. 5 quantitatively illustrate the benefits of using a vacuum on a solid feed containing lignin before increasing the pressure on the slurry. The vacuum can be applied simultaneously with shear and agitation via the conveying screw. The minimum time to maintain the application of vacuum is sufficient to disperse the particles to more than 50% of the theoretical dispersion at 25 ° C, more preferably more than 75% dispersion at 25 ° C, A dispersion of greater than 90% is most preferred. It is preferred that the solid raw material comprising lignin be surrounded or included by the slurry liquid for sufficient effectiveness of the vacuum. In a preferred embodiment, the slurry liquid is water. In another embodiment, the slurry liquid includes 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 the sample after 2 minutes of settling. If 16 grams of solid is present in 84 grams of liquid, the dry matter content at 100% dispersion is 16%. At 50% of theoretical dispersion, the dry matter content of the sample after 2 minutes of settling is 8%.

  The final policy of creating a slurry containing lignin that does not place lignin conversion simultaneously with pretreatment and fermentation of lignocellulosic biomass (10) is to include a slurry liquid, preferably a solid feed containing lignin in water, containing lignin Exposure to high shear, such as that found in a blender, which further disperses the raw material particles over time throughout the slurry. In another embodiment, the slurry liquid is a hydrogen donor.

  In most instances, the slurry liquid is water or water in combination with at least one hydrogen donor. The ratio of the amount of water in the slurry liquid to the dry weight of the lignin raw material is preferably in the range of 0.3 to 9, more preferably 0.5 to 9, and even more preferably 1 to 9. 2 to 9 are more preferred ratios, and 3 to 5 are even more preferred ratios.

Slurry creation experiment An experiment was conducted to evaluate slurry preparation under vacuum treatment compared to slurry preparation under standard mechanical agitation.

Slurry production experiment 1
A 450 g quantity of lignin-rich composition with 53% dry matter was inserted into a 3 liter round bottom flask with 1050 g of water to give a theoretical concentration of 16% of the dry product of lignin-rich composition in the mixture. Reached. No mechanical mixing was applied.

  The flask had a size of about 16 cm and was equipped with a stirrer having a size of about 6 cm.

  The flask was sealed and a 29.8 mm Hg vacuum was applied for 5 minutes and removed. After a 2 minute settling time, a first sample of the slurry containing lignin was extracted.

  Mechanical stirring was applied to the slurry containing lignin for 1 minute at atmospheric pressure, then the mechanical stirring was stopped and the sample was extracted after a settling time of 2 minutes. The mechanical agitation procedure was repeated for an additional 5, 10, 30, and 60 minutes of agitation time, and samples were extracted after a settling time of 2 minutes each time.

  There was no lump at the bottom of the flask, and the slurry containing lignin appeared to be uniformly mixed.

Slurry production experiment 2
A theoretical concentration of 16% dry matter of the lignin-rich composition in the mixture by inserting a 450 g quantity of lignin-rich composition with 53% dry matter into a 3 liter round bottom flask with 1050 g of water. A control experiment was realized by reaching.

  The flask and mechanical stirrer were the same as in the experiment performed using vacuum. The slurry containing lignin was subjected to mechanical stirring only and samples were extracted after 5, 1, 5, 10, 30, 60 minutes of stirring. The mechanical stirring was stopped for 2 minutes before each sampling.

  A relevant amount of lumps was present at the bottom of the flask and the slurry containing lignin appeared heterogeneous.

  Mechanical agitation was obtained by agitating the slurry containing lignin at 250 rpm in both experiments.

  The dry matter concentration of the lignin-rich composition was measured by drying the sample in an oven at 105 ° C. for 15 hours.

  FIG. 5 reports a graph of percent complete dispersion of the lignin-rich composition in a slurry containing lignin. The percent complete dispersion is the dry matter concentration of the lignin-rich composition in the slurry containing lignin normalized with respect to the theoretical concentration.

  The experiment shows that by applying a vacuum, the time required to obtain a complete dispersion of the lignin-rich composition in the slurry containing lignin is significantly reduced, thereby reducing mixing energy, time savings and It is demonstrated that the slurry tank volume can be reduced.

Slurry Pressurization and Transport After creating a slurry containing lignin, it is fed from the lignin conversion reactor pressure and slurry pump outlet to the lignin conversion reactor so that the slurry can be charged into the lignin conversion reactor (500). The pressure should be slightly higher than the pressure to (500).

  The slurry containing lignin can be pressurized using a slurry pump (400). For purposes herein, the term slurry pump (400) is meant to refer to any pump that can reach the desired pressure, eg, a piston pump and / or a syringe pump. Multistage centrifugal pumps can also reach the required pressure. A slurry pump (400), shown as a piston pump used in this experiment, has an inlet valve (350). The inlet valve position can range from fully open to fully closed. Thus, the inlet valve position can be selected from the group consisting of an opening, a closing and at least a partial opening, where the opening is a full opening (the restriction over the valve measured by the pressure drop is the smallest possible). Means closed, meaning that neither liquid nor gas flows through the valve, and at least a partial opening means that the valve is not fully closed and fully open, Means somewhere in between. The slurry pump (400) has an outlet valve (450). The outlet valve may exist at an outlet valve position selected from the group consisting of an opening, a closing and at least a partial opening, where the opening, the closing and the at least partial opening have the same meaning as for the inlet valve position. Have.

  The slurry pump (400) further includes a piston (420) and a piston chamber (425). The piston (420) forms a pump cavity forming a seal inside and to the piston chamber (425). The size of the cavity depends on where the piston (420) is in the piston chamber (425).

  At least a portion of the piston (420) from the piston chamber (425) through the slurry containing lignin through an inlet valve (350) present at an inlet valve position selected from the group consisting of at least a partial opening and an opening (430A) Flow into the pump cavity formed by pulling. During this inlet step, the outlet valve (450) is in the closed outlet valve position (440B). The pump cavity is at the inlet pump cavity pressure. After a slurry containing a certain amount of lignin flows into the pump cavity, the inlet valve position is switched to closed (430B), or in other words, the inlet valve is closed. The force is then applied to the piston (420) in the piston chamber (425) until the pressure of the slurry containing lignin reaches a discharge pressure higher than the reactor operating pressure, also known as lignin conversion reactor pressure or deoxygenation pressure. Place or apply. The reactor operates in the range of 80 to 245 bar, 80 to 210 bar, 90 to 210 bar and 90 to 175 bar. Therefore, the pump discharge pressure should also be within the above ranges of 80 to 245 bar, 80 to 210 bar, 90 to 210 bar and 90 to 175 bar, but should be higher than the lignin conversion pressure. It should also be noted that for purposes of this specification, the terms lignin conversion vessel and lignin conversion reactor are interchangeable.

  By opening the outlet valve (450), ie, switching the outlet valve position to a position selected from the group consisting of at least partial openings and openings, at least a portion of the slurry containing lignin is discharged from the pump cavity. To do. The piston (420) is further pressed into the pump body to reduce the volume of the pump cavity and push at least a portion of the slurry containing lignin through the outlet valve (450). The outlet valve (450) is connected to the lignin conversion reactor (500) by a tube, pipe or other connection. Connected to the lignin conversion reactor means that the material from the pump cavity flows through the outlet valve, generally through a pipe, tube, or through a series of connecting pipes or tubes into the lignin conversion reactor (500). It means you can. In one embodiment, there may be a plurality of additional valves between the outlet valve and the lignin conversion reactor (500), for example, a valve for shutting off the lignin conversion reactor (500).

  In order to run the process in a continuous manner, it is not necessary to continuously introduce a slurry containing lignin into the lignin conversion reactor (500). For example, if only one piston pump is used, a slurry containing lignin is introduced into the lignin conversion reactor (500) in steady aliquots or pulses. Therefore, there is a period when there is no product flowing into the lignin conversion reactor. However, over time, the mass introduced into the lignin conversion reactor is equal to the mass removed from the lignin conversion reactor. One distinguishing feature between continuous and batch processes is that in a continuous process, a slurry containing lignin is introduced into the lignin conversion reactor (500) and / or the lignin conversion product is lignin conversion reaction. The reaction is taking place or proceeding simultaneously with removal from the vessel. Another approach to describe this is to perform conversion (eg, deoxygenation, or hydrogenation) in a lignin conversion reactor while simultaneously or together from the lignin conversion reactor (500) of the lignin conversion reactor contents. It is to take out at least a part. Such removal is performed in a continuous manner including aliquots or pulse removal.

  The prior art proposes the use of piston pumps or syringe pumps for high pressure reactor charging. However, the consensus of the art is the use of a check valve. This simple and sophisticated approach has been used for many years. However, as discovered by the inventors, check valves and other valve configurations do not work for slurries containing lignin. The present inventors consulted with multiple pump and valve experts to evaluate a number of solutions proposed by the experts, all of which continued the slurry containing lignin into the lignin conversion reactor. Could not be charged. The pressure could not be maintained or could not be maintained for a long time. Observations have shown that rugged, fibrous lignin clogs lignin from slurries containing lignin in the valve seat and accumulates in areas of low flow or high impact, causing valve embolization.

  It has been discovered that more complex valve systems work. The use of industry standards and simple check valves should be replaced with valves with controllable positions, and the valves are non-restricted and non-occluded of slurry containing lignin through the valve or its flow path It was discovered that a flow should be provided. Non-restricted flow means that the flow of slurry containing lignin through the valve (channel) does not, for example, bend and change direction, and does not increase at a linear rate, for example, in channel reduction. Non-occlusive flow is the path of the slurry flow where the flow path is such that any additional element, for example, the valve is in a fully open position, the slurry must flow around or impinge upon the additional element. This means that it does not contain any butterfly valve inserts. Furthermore, the flow path does not contain additional dead zones, for example, valve seat grooves for gate valves. The dead zone, for example, the valve seat groove of a gate valve, is filled with slurry when the valve is opened, and when the valve is closed, the partition compresses the slurry into the groove and of the slurry containing lignin in the groove. Allows accumulation and compression. In this case, the valve does not sit or seal over time and cannot maintain pressure.

  By way of example and not limitation, valves that provide unrestricted and non-occlusive flow of slurry containing lignin include ball valves, full port ball valves or full port fixed ball valves. In contrast, conventional valves, such as most ball valves, most angle valves, most diaphragm valves, most butterfly valves, and most check valves limit and / or block the flow of slurry containing lignin. However, lignin from slurries containing lignin can accumulate in areas of low flow or high impact, eventually causing valve embolization, or neither seating nor sealing, and cannot hold pressure (that Examples of such valves are described in Chemical Engineers' Handbook, Fifth Edition, Perry & Chicago, p 6-54 to 6-57, 1973). In fact, this accumulation of lignin from a slurry containing lignin can occur quite rapidly, and in some cases it is too rapid so that the slurry containing lignin passes through the inlet valve and is not charged into the pump cavity at all (slurry pump Transport experiment 1).

  By removing the check valves, the system was no longer automatic within the valves, but required special additional control to open and close each valve in a synchronized fashion. Thus, contrary to the prior art and many times the pump and valve experts have proposed to the inventors, the process is such that the inlet valve (350) and outlet valve (450) are not check valves. It worked only when it was a valve that provided unrestricted and non-occlusive flow (a check valve is a valve that prevents backflow). The pressurization process, discharge and final charge into the reactor preferably lack any check valve in the slurry flow path. Alternatively, the slurry flows through the check valve and into the slurry pump (400) and does not enter the reactor.

  Different embodiments are available. For example, there can be a plurality of slurry pumps including at least two piston pumps. If there are two piston pumps, each piston pump may have its own inlet valve and its own outlet valve (eg, the first piston pump may have a first inlet valve (350A) and a second outlet valve). One 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. Two piston pumps in a parallel configuration can 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.

  Finally, at least a portion of the slurry containing lignin, some in solid form, is introduced into the lignin conversion reactor (500). The lignin conversion reactor has a lignin conversion pressure and a lignin conversion temperature. The lignin conversion pressure is at least slightly lower 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. Generally, the slurry pump discharge pressure is higher than the lignin conversion pressure, which is greater than the lignin conversion reactor pressure and the absolute amount of pressure drop during the process from the slurry pump discharge to the lignin conversion reactor (500). Is also expensive.

Slurry Pump Transport Experiment An experiment was conducted in which slurry containing lignin was charged into a pressurized lignin conversion reactor. Unless stated differently, the following procedure was applied to all experiments.

  Deionized water was added to the lignin-rich composition obtained from the pretreatment of lignocellulosic biomass to obtain a slurry containing 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 mixed thoroughly intermittently for 1 to 2 minutes to obtain a uniform slurry. The uniformity of the slurry was evaluated with the naked eye. The slurry was inserted into the mixing vessel (340) and stirring was continued. The mixing vessel (340) is a stainless steel dish-bottom vessel having a volume of about 1 L that houses a standard laboratory paddle mixer and a bottom discharge port connected to a Chandler Quizix QX dual syringe pump with two pump cavities. Met. An inlet valve (350) was inserted between the mixing 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 pipe connection to a Parr 4575 reactor equipped with two 45 ° inclined turbine blades, cooling coils, separate gas and slurry supply ports, and a discharge dip tube (610). . An outlet valve (450) was inserted between the two pump cavities of the Chandler Quizix QX dual syringe pump and the Parr reactor. 200-400 scfh of hydrogen was inserted into the Parr reactor at a temperature of 20 ° C. to reach a pressure of 48.3 bar. The Parr reactor was heated to a temperature corresponding to 90% of the reaction temperature and a continuous flow of hydrogen was started into the Parr reactor. The final temperature and pressure in the Parr reactor varied from 275 to 325 ° C. and from 100 to 175 bar. The pressure was measured by a pressure transducer (Ashcroft Type 62) connected to a Parr reactor.

  By switching the inlet valve position of the first inlet valve (350A) corresponding to the first pump cavity to the open position (430A) by the actuator, the slurry containing lignin is transferred from the mixing tank (340) to the Handler Quizix QX dual syringe. Flowed into the first pump cavity of the two pump cavities of the pump. After the slurry containing lignin reached the first pump cavity, the first inlet valve (350A) corresponding to the first pump cavity was switched to the closed inlet valve position (430B) by the actuator. After closing the first inlet valve (350A) corresponding to the first pump cavity, the inlet valve position of the second inlet valve (350B) corresponding to the second pump cavity is moved to the open position (430A) by the actuator. By switching, the slurry containing lignin was flowed from the mixing vessel (340) into the second pump cavity of the two pump cavities of the Chandler Quizix QX dual syringe pump.

  After closing the first inlet valve (350A) corresponding to the first pump cavity (430B), the Handler Quizix QX dual syringe pump causes the slurry containing lignin to flow from the pressure of the Parr reactor in the first pump cavity. Was also pressurized to a high pressure. While the slurry containing lignin in the first pump cavity was pressurized, both the first inlet valve (350A) and the first outlet valve (450A) were closed. After pressurizing the slurry containing lignin in the first pump cavity to a pressure higher than that of the Parr reactor, the first outlet valve (450A) corresponding to the first pump cavity is set to the open position (440A). The actuator was switched to allow the slurry containing pressurized lignin in the first pump cavity to be charged into the Parr reactor.

  After opening the first outlet valve (450A) corresponding to the first pump cavity, the second inlet valve (350B) corresponding to the second pump cavity was switched to the closed position (430B) by the actuator. After closing the second inlet valve (350B) corresponding to the second pump cavity (430B), the Handler Quizix QX dual syringe pump removes the slurry containing lignin in the second pump cavity from the pressure of the Parr reactor. Was also pressurized to a high pressure. While the slurry containing lignin in the second pump cavity was 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. After pressurizing the slurry containing lignin in the second pump cavity to a pressure higher than that of the Parr reactor, the first outlet valve (450A) corresponding to the first pump cavity is set to the closed position (440B). It switched with the actuator. After closing the first outlet valve (450A) corresponding to the first pump cavity, the second outlet valve (450B) corresponding to the second pump cavity is switched to the opening (440A) position by the actuator, and the second The slurry containing pressurized lignin in the pump cavities was allowed to be charged to the Parr reactor.

  After opening the second outlet valve (450B) corresponding to the second pump cavity, the first inlet valve (350A) corresponding to the first pump cavity is switched to the opening position (430A) by the actuator, and the mixing tank From (340), it was possible to pressurize the slurry containing additional lignin entering the first pump cavity and subsequent charge to the Parr reactor.

Slurry pump transport experiments 1 and 2
For slurry pumping experiments 1 and 2, the inlet and outlet valves were small orifice valve stem lift valves from Vindum Engineering, model number CV-505-SS. These valves were recommended by experts in the field of slurry pumping and were shown to be sufficient to charge a slurry containing lignin into a pressurized reactor.

  For Experiment 1, when the inlet valve corresponding to the first pump cavity was switched to the open position, it was immediately plugged with solid lignin from the slurry containing lignin. The slurry containing lignin did not reach the first pump cavity, the outlet valve corresponding to the first pump cavity, nor the Parr reactor at all.

  For Experiment 2, experts in the field of slurry pumping help pressurize the mixing vessel (340) from 2.5 to 3 bar and charge the slurry containing lignin through the inlet valve into the pump cavity. Recommended. Experts have shown that pressurization of the mixing vessel (340) allows slurry containing lignin to flow through the inlet valve and into the pump cavity without plugging the inlet valve. When the inlet valve corresponding to the first pump cavity is switched to the open position, it is immediately plugged by solid lignin from the slurry containing lignin, so that any amount of slurry containing lignin can enter the first pump cavity, Neither the outlet valve nor the Parr reactor was reached.

Slurry pump transport experiments 3 and 4
For Runs 3 and 4, experts in the field of slurry pumping recommended replacing the inlet and outlet valves with Swagelock bellows seal valves, model number SS-HBS6-C. The inlet and outlet valves of Experiments 3 and 4 have larger orifices than those of Experiments 1 and 2, and experts have shown that these larger orifices do not plug the inlet valve with slurry containing lignin. It is possible to flow through the pump cavity.

  For Experiment 3, when the inlet valve corresponding to the first pump cavity was switched to the open position, it enabled the charging of a portion of the slurry containing lignin entering the first pump cavity into the Parr reactor. did. However, after a period of 15 to 20 minutes, the inlet valve was plugged again with solid lignin from the slurry containing lignin.

  For Experiment 4, experts in the field of slurry pumping help pressurize the mixing vessel (340) between 2.5 and 3 bar and load it into the pump cavity through a slurry inlet valve containing lignin. Recommended to do. Experts have again shown that pressurization of the mixing vessel (340) allows slurry containing lignin to flow through the inlet valve and into the pump cavity without plugging the inlet valve. When the inlet valve corresponding to the first pump cavity was switched to the open position, it enabled a portion of the slurry containing lignin entering the first pump cavity to be charged to the Parr 4575 reactor. However, after a time of 25 to 30 minutes, the inlet valve was re-embedded with solid lignin from the slurry containing lignin.

Slurry pump transport experiments 5 and 6
For Experiment 5, the inventors decided to replace the inlet valve with a Swagelok 60 series 3-piece ball valve, model number SS-62TS6. The outlet valve was the same Swagelock bellows seal valve used in experiments 3 and 4. When the inlet valve corresponding to the first pump cavity is switched to the open position, it passes a portion of the slurry containing lignin entering the first pump cavity to the outlet valve corresponding to the first pump cavity. And allowed to enter the Parr reactor. This process was carried out for a period of about 2 days, at which time the outlet valve was plugged with solid lignin from a slurry containing lignin.

  For Experiment 6, the inlet valve was the same Swagelok 60 series 3 piece ball valve used in Experiment 5, but we used an outlet valve for the Swagelok 60 series 3 piece ball valve, model number SS-62TS6. And decided to replace it. When the inlet valve corresponding to the first pump cavity is switched to the open position, it passes a portion of the slurry containing lignin entering the first pump cavity to the outlet valve corresponding to the first pump cavity. And allowed to enter the Parr reactor. The pump could then continuously charge the slurry containing lignin into the Parr reactor without plugging the inlet and outlet valves. It was not necessary to pressurize the mixing vessel (340) and charge it into the reactor.

Carbide prevention One of the difficulties in any continuous lignin conversion process is to avoid the formation of carbides. Carbide formation results in reduced yields of lignin conversion products and disrupts the continuity of the lignin conversion process. This is because the lignin conversion process must be shut down and the carbides removed from the lignin conversion reactor before the process can continue.

In order to avoid carbides, we perform deoxygenation, which is the exposure of lignin to hydrogen as H ₂ gas or via a hydrogen donor at the lignin conversion temperature and the lignin conversion pressure, The boiling point of the liquid composition in the reactor at atmospheric pressure is in the range below the critical temperature of the liquid composition, and the lignin conversion pressure is higher than the bubble pressure of the liquid composition in the reactor at the lignin conversion temperature. It has been found that it is high, provided that the lignin conversion pressure is selected to avoid the formation of carbides.

  The liquid composition of the reactor is a liquid component composition added to the vessel. For example, in one embodiment, the liquid composition is substantially pure water with dissolved species. In the case of pure water, hydrogen comes from the added hydrogen gas. For pure water or substantially pure water, the bubble pressure is the vapor pressure of water at the lignin conversion temperature. In another embodiment, the liquid composition can include water and a hydrogen donor. This liquid composition has its own bubble pressure and critical temperature forming the lower and upper boundaries of the temperature range, provided that the lignin conversion pressure is selected to avoid carbide formation after two residence cycles. This can be further confirmed visually by opening the reactor after two residence cycles and observing the presence or absence of carbides (dark residue covering the reactor). The reactor also lacks any liquid.

  It has been discovered that lignin conversion pressure is also a function of the amount of gas exiting the reactor. The greater the amount of gas used, for example hydrogen gas or nitrogen, the higher the required pressure. In the case of hydrogen donors, a small amount of gas is used and therefore lower lignin conversion pressure is required to prevent carbides.

  A suitable lower lignin conversion pressure can be easily established experimentally as follows. The liquid composition charged to the reactor can be determined. In most cases it is water from the slurry, and if present, any hydrogen donor compound is used. The design includes a flow rate for the gas exiting the reactor. While the calculation can be performed manually, a commercially available simulation package can be used to determine the vapor-liquid equilibrium conditions (bubble pressure) of the liquid mixture. This is demonstrated in Table 2, which is “calculated reactor pressure for liquid water” using water as the liquid. As can be seen from the table, the theoretical calculation is a fairly close approximation, but in the case of water, the actual pressure is still higher than the amount calculated based on the pure components. Once the approximation is determined, the reaction can be carried out in two residence cycles, the vessel opened and tested for carbides. If carbide is present, the reaction pressure is increased until no carbide is present, so that no carbide is formed after two residence cycles.

  The 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 charged at a volumetric flow rate at operating conditions of 1 L / hour, the residence cycle is 4 hours and the two residence cycles are 8 hours. At 2 L / hour, the residence cycle is 2 hours and the two residence cycles are 4 hours.

  As described above, the lignin conversion process should be performed at the lignin conversion temperature, which is higher than the boiling point of the slurry liquid at atmospheric pressure and within a range below the critical temperature of the slurry liquid, provided that the lignin conversion process The condition is that the pressure is higher than the bubble pressure of the slurry liquid at the lignin conversion temperature and the lignin conversion pressure is selected to avoid the formation of carbides.

  To avoid carbide formation, the lignin conversion pressure should be selected such that the lignin conversion pressure is higher than the bubble pressure of the slurry liquid at the lignin conversion temperature. The bubble pressure is the sum of the partial vapor pressures of all components in the lignin conversion reactor.

  If the slurry liquid contains water, the lignin conversion process should be performed at a lignin conversion temperature below the critical temperature of water.

  Generally, the lignin conversion process is performed at a lignin conversion temperature within the range of 190 ° C to 370 ° C. The lignin conversion temperature ranges are preferably 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 from the group consisting of 300 ° C to 330 ° C.

  When the slurry liquid contains a hydrogen donor, the lignin conversion process can be performed at a lignin conversion temperature in the range of 190 ° C. to 350 ° C., more preferably 200 ° C. to 310 ° C., more preferably 210 ° C. to 300 ° C. Preferably, 210 ° C to 280 ° C is most preferable.

  The hydrogen donor can also be introduced into the lignin conversion reactor separately from the liquid slurry. Hydrogen donors can also arise from the carbohydrate conversion step, and thus lignocellulosic biomass is producing its own hydrogen that is used in the process. In such a process, a hydrogen donor, such as ethylene glycol, can be produced in the carbohydrate conversion step of FIG. 3, run into a liquid slurry, and introduced into the lignin conversion reactor via stream 325.

  It is also important to control the above lignin conversion pressure in order to avoid carbides. The lignin conversion pressure is preferably in a range 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.

  Continuous lignin conversion in the presence of carbohydrate should be performed at a lignin conversion pressure higher than the theoretical equilibrium vapor pressure of water at the lignin conversion temperature. It was directly observed that carbides formed when the lignin conversion pressure was even higher than the calculated water vapor pressure at the lignin conversion temperature and contributed to the effluent gas sweeping the top of the liquid. When the lignin conversion pressure was substantially higher than the calculated water vapor pressure at the lignin conversion temperature, no carbide was observed. In order to avoid carbide formation in a continuous process, it was necessary to maintain at least a portion of the reactor contents as liquid, but to do so it was much higher than expected or expected It was discovered that pressure was required.

  Carbide formation is not seen in batch reactor conditions. This is because batch reactor conditions are always in theoretical equilibrium. When the gas sweeping the outlet is introduced in a continuous process, the equilibrium conditions no longer exist and the pressure required to maintain at least some of the reactor contents as liquid in the lignin conversion reactor is conventional. Substantially higher than the teachings of wisdom or innovation. While process simulation can be performed initially to approximate the lignin conversion pressure at a given condition, the actual minimum lignin conversion pressure is easily established experimentally by increasing the pressure until no carbides are observed. can do. The practitioner of the present invention notes that the increase in pressure can be highly dependent on the flow rate from the reactor.

Carbide prevention experiments Unless otherwise stated, the following procedure was applied to all experiments.

  Deionized water was added to the lignin-rich composition obtained from the pretreatment of lignocellulosic biomass to obtain a slurry containing 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 mixed thoroughly intermittently for 10 minutes to obtain a uniform slurry. The uniformity of the slurry was evaluated with the naked eye. The slurry was inserted into the mixing tank and stirring was continued. The mixing vessel was a stainless steel pan bottom vessel with a bottom outlet port connected to a Chandler Quizix QX dual syringe pump with two pump cavities. An inlet valve was inserted between the mixing tank and the two pump cavities of the Chandler Quizix QX dual syringe pump. The Chandler Quizix QX dual syringe pump was connected by pipe connection to a Parr 4575 reactor equipped with two 45 ° inclined turbine blades, cooling coils, separate gas and slurry supply ports, and a discharge dip tube. The outlet valve was inserted between the two pump cavities of the Chandler Quizix QX dual syringe pump and the Parr reactor.

  Hydrogen was inserted into the Parr reactor at a temperature of 20 ° C. to reach a pressure of 48.3 bar. The Parr reactor was heated to a temperature corresponding to 90% of the reaction temperature and a continuous flow of hydrogen was started into the Parr reactor. The pressure was measured by a pressure transducer (Ashcroft Type 62) connected to a Parr reactor.

  By passing the lignin-containing slurry from the mixing vessel through a Chandler Quizix QX dual syringe pump by opening and closing the inlet and outlet valves to allow the lignin-containing slurry to flow continuously into the Parr reactor. Flowed into the reactor.

  The experiment was performed according to the described procedure. Experimental parameters are reported in Table 1.

  In the reaction products of Experiments 1 to 3, a large amount of carbide without liquid water was observed. In Experiments 4-8, carbides and liquid water were not observed.

  In order to proceed the reaction as opposed to decomposition, it may be necessary to have the liquid present, eg liquid water.

  Even if the reactor was operated at a total system (reactor) pressure sufficiently higher than the vapor pressure of water at 340 ° C. (146.1 bar) relative to the gas pressure, there was still no water or solvent present. It was discovered.

Catalyst residence and separation Since the lignin conversion catalyst exists as free particles (625) and is not a fixed bed, the lignin conversion catalyst needs to be separated from the lignin conversion product. The catalyst particles (625) are liquid after the liquid lignin conversion product is removed from the lignin conversion reactor (500) by filtration, sedimentation, centrifugation, solid bowl centrifugation, cyclonic treatment or other processes known in the art. It can be separated from the lignin conversion product. The separated catalyst is then reintroduced into the lignin conversion reactor for further reaction, processed for replenishment and then reused or discarded. These conventional methods are known.

  It has been discovered that the free catalyst particles (625) can be separated in situ from the lignin conversion products present in the lignin conversion reactor (500) while performing continuous catalytic conversion of the lignin feedstock to lignin conversion products. It was. Thus, the lignin conversion product can be separated from the catalyst particles (625) during the continuous catalytic conversion of the lignin feedstock to the lignin conversion product.

  This separation is done by gravity settling, and the fluid linear velocity (meters / minute) of the lignin conversion products (liquid and gas) exiting the lignin conversion reactor is the catalyst in the liquid / gas lignin conversion product stream exiting the reactor. Less than the gravitational linear settling velocity of the particles (625). Thus, the lignin conversion product removed from the lignin conversion reactor is higher than the liquid level in the lignin conversion reactor and at a linear velocity below the settling velocity of the catalyst particles (625) (relative to gravity). As long as it is removed from the site, the catalyst particles remain in the lignin conversion reactor.

  The liquid level of the lignin conversion reactor is at the physical interface between the bulk liquid phase and the bulk gas phase in the lignin conversion reactor (500). The bulk gas phase is a continuous gas phase having a specific gravity less than that of the bulk liquid phase. The bulk gas phase can have droplets in the bulk gas phase. Similarly, the bulk liquid phase is a continuous liquid phase and has dissolved gases and bubbles.

  The height relative to the liquid level at which the lignin conversion product is removed from the lignin conversion reactor is referred to as the separation height. The separation height is higher than the catalyst particle moving height, which is the height that the catalyst particles (625) reach when transported with the lignin conversion product. Since the sedimentation rate of the catalyst particles is larger than the removal rate of the lignin conversion product, at least the majority of the catalyst particles (625) do not reach the point where the lignin conversion product is taken out from the lignin conversion reactor. The catalyst particles (625) will eventually fall back into the lignin conversion reactor (500) as long as the inside desorption height is sufficiently large relative to the travel height.

  In fact, as long as the settling rate of the catalyst particles is substantially greater than the liquid lignin conversion product removal rate, at least the majority of the catalyst particles (625) will remove the liquid lignin conversion product from the lignin conversion reactor. It should be large enough not to reach the extraction point. For example, if the liquid lignin conversion product is removed through an “L” shaped dip tube having the dip tube long side length (612) and dip tube short side length (614) shown in FIG. The dip tube short side length (614) must be less. When the dip tube short side length (614) is 1 meter, the sedimentation rate of the catalyst particles is 1.2 meters per second, the liquid lignin conversion product removal rate is 1 meter per second, and the liquid lignin conversion product is The separation height (which is also the dip tube short side length (614)) is reached after 1 second. Since the catalyst particles (625) have a settling velocity of 0.2 meters per second, which is greater than the liquid lignin conversion product velocity, the catalyst particles (625) will move at a speed (this rate of movement of the liquid lignin conversion product above the dip tube. Move above the dip tube (610) at a speed of 0.2 meters per second (less than 0.8 meters per second in the examples). As a result, if the liquid lignin conversion product reaches a separation height of 1 meter (also dip tube short side length (614)) after 1 second, the catalyst particles (625) have moved 0.8 meters. Only. In this way, the catalyst particles do not reach the separation height and “settling” again in the lignin conversion reactor (500).

  Conversely, if the sedimentation rate of the catalyst particles is less than the liquid lignin conversion product removal rate, the catalyst particles (625) reach or exceed the withdrawal height and are removed from the reactor. For example, if the sedimentation rate of the catalyst particles is 0.8 meters per second and the liquid lignin conversion product removal rate is 1 meter per second, the catalyst particles (625) move at a speed that is at least equal to the liquid lignin conversion product. . In this way, the catalyst particles reach a disengagement height at least simultaneously with the liquid lignin conversion product, thereby being removed from the lignin conversion reactor (500) through the dip tube (610).

  In a preferred embodiment, the lignin conversion reactor has a stirring zone and a sedimentation zone, also known as a decantation zone. In the settling zone, the reactor liquid phase is exposed to weaker agitation than in the agitation zone. The settling zone can be created by using the following dip tube. The interior of the dip tube is subjected to very weak agitation and is therefore a settling zone in that embodiment. The settling zone can also be created by placing a baffle plate above the stirrer but below the liquid level to create a stationary spot. Another approach is to have a separate reactor or vessel that does not have agitation. This configuration is described in the bubble column section. The lignin conversion product is removed from the sedimentation zone at the lignin conversion product removal rate. For more efficient removal of the catalyst, the lignin conversion product removal reaches a point in the lignin conversion reactor that is higher in gravity than the liquid level of the lignin conversion reactor, so that the lignin conversion product is in the stirring zone. Conditioned on having to flow through a part of the sedimentation zone.

  FIG. 4 demonstrates one embodiment of this principle. In this embodiment, the product must be removed via the dip tube (610) and the lignin conversion product must flow out above the dip tube. As the lignin conversion product moves up the tube, the first catalyst particles (625) move with it. However, the first catalyst particles have a final or settling rate that is the rate at which the particles descend through the liquid lignin conversion product of the reactor. When catalyst particles (625) exiting the dip tube (610) are observed, the first catalyst particles descend below the tube and thus gravity at a rate less than the rate at which the catalyst is retained in the reactor. In contrast, it is easy to increase the diameter of the dip tube to reduce (decelerate) the lignin conversion product velocity relative to gravity so that the conversion product moves above the tube. If it is desirable to purge the catalyst, or if it is desirable to add fresh catalyst so that the old catalyst can be removed, the tube diameter is reduced (flow rate increased) and the lignin conversion reactor (500 ) From the catalyst particles (625) stream. Catalyst removal and replenishment can be performed continuously so that a predetermined percentage of the catalyst is removed and replenished on a continuous basis.

  Indeed, the catalyst particles (625) vary in size and shape, each having a different settling rate. Thus, a preferred lignin conversion product removal rate is less than a settling rate of at least 75% by weight of the catalyst particles, a lignin conversion product removal rate of at least less than 85% by weight of the catalyst particles is more preferred, Even more preferred is a lignin conversion product removal rate of at least 90% by weight below the settling rate, even more preferred is a lignin conversion product removal rate of at least 95% by weight of the catalyst particles, and 100% by weight of the catalyst particles. Most preferred is a lignin conversion product removal rate less than the settling rate.

“75% by weight of 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 catalyst in the reactor is removed. . Or the percentage is
100 * R / [R + X]
And
Where R is the weight of catalyst remaining and X is the weight of catalyst leaving or removed from the reactor. 100 makes the number a percentage.

  One skilled in the art will now readily see how a properly designed system can be continuously replenished with catalyst, for example, 5% by weight can be removed while 5% by weight fresh catalyst is added. I can understand. Thus, the catalyst is continuously turned over.

Catalyst residence experiment An experiment was conducted in which the catalyst was retained in the reactor. Unless stated differently, the following procedure was applied to all experiments.

  Deionized water was added to the lignin-rich composition obtained from the pretreatment of lignocellulosic biomass to obtain a slurry containing 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 mixed thoroughly intermittently for 10 minutes to obtain a uniform slurry. The uniformity of the slurry was evaluated with the naked eye. The slurry was inserted into the mixing vessel (340) and stirring was continued. The mixing vessel (340) was a stainless steel pan bottom vessel with a bottom discharge port connected to a Chandler Quizix QX dual syringe pump with two pump cavities. An inlet valve (350) was inserted between the mixing tank (340) and the two pump cavities of the Chandler Quizix QX dual syringe pump. The Chandler Quizix QX Dual Syringe Pump is a stainless steel discharge dipping with two 45 ° inclined turbine blades, cooling coils, separate gas and slurry supply ports, 0.25 inch outer diameter and 0.152 inch inner diameter Linked by pipe connection to a Parr 4575 reactor equipped with a pipe (610). The outlet valve was 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 Might Mite model 91 back pressure regulator (BPR) located in the lignin conversion reactor discharge line between the Parr reactor and the product receiver. The lignin conversion pressure was measured by a pressure converter (Ashcroft Type 62) connected to a Parr reactor.

  The experiment was started after the Parr reactor was charged with 150 mL of deionized water. The lignin conversion reactor pressure was increased to 48.3 bar with 20 ° C. hydrogen. After the lignin conversion reactor was heated to 90% of the lignin conversion temperature, the slurry containing lignin was charged into the lignin conversion reactor. After increasing the temperature to 90% of the lignin conversion temperature, additional deionized water is passed from the mixing tank (340) through a Chandler Quizix QX dual syringe pump into the lignin conversion reactor (500) at 2.8 mL / min. Flowed at speed. A hydrogen stream was added to the lignin conversion reactor at a rate of 150 seem. At this point, the temperature in the lignin conversion reactor was increased to 100% of the lignin conversion temperature and the lignin conversion reactor pressure was adjusted to the desired operating pressure reflected in this experiment via BPR.

  The slurry containing lignin was then charged to the reactor through a Handler Quizix QX dual syringe pump at a rate of 2.8 mL / min. The slurry containing lignin is removed from the Mixer Quizix QX from the mixing vessel (340) by opening and closing the inlet valve (350) and outlet valve (450) to allow the lignin slurry to flow continuously into the Parr reactor. It was passed through a dual syringe pump and flowed into a Parr reactor. The lignin conversion product was continuously removed from the lignin conversion reactor (500) via the dip tube (610), cooled to about 35 ° C. and then passed through BPR. After flowing through the BPR, the lignin in a stainless steel product receiver fitted with a vent line to allow non-condensable gas from the lignin conversion reactor to be separated from the liquid lignin conversion product. The conversion product was recovered.

  The lignin conversion reactor allowed to reach steady state conditions, and after four reactor residence cycles, the lignin conversion product was recovered in the product receiver in about one additional reactor residence cycle. At this time, all feed streams to the lignin conversion reactor were stopped and the lignin conversion reactor was shut off from the product receiver by a shut-off valve. The lignin conversion reactor was cooled to about 30 ° C. and the pressure was reduced to atmospheric pressure by opening a vent valve.

  The liquid lignin conversion product was mixed with an equal amount of methyl tertiary butyl ether (MTBE). The mixture was filtered through a Buchner funnel fitted with Whatman # 1 filter paper.

Catalyst retention experiment 1
For Experiment 1, the sponge nickel catalyst was added directly to the slurry containing lignin, resulting in a slurry containing 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 10 to 40 μm. The lignin conversion reactor was operated at 340 ° C. and 156.4 bar, which is about 10 bar higher than the water vapor pressure at 340 ° C. Under the operating conditions, the average residence time of the slurry containing lignin was 53 minutes.

  Surprisingly, after stopping the experiment and filtering the liquid lignin conversion product, very little catalyst was observed on the filter paper and in one example no catalyst was observed. When the catalyst was observed on the filter paper, it was observed as catalyst fines. When the Parr reactor was shut down and opened, it was surprisingly observed that almost all of the catalyst remained in the lignin conversion reactor.

Catalyst retention experiment 2
For Experiment 2, 28 g of sponge nickel catalyst on a dry basis was charged directly to the Parr reactor with the first 150 mL of deionized water before the experiment was started. Prior to charging the slurry containing lignin into the lignin conversion reactor, no catalyst was added to the slurry containing lignin. As a result, the slurry containing lignin contained 15 weight percent lignin on a dry basis. The lignin conversion reactor was operated at 173.4 bar, which was about 17 bar higher than the water vapor pressure at 340 ° C. and 340 ° C. The hydrogen flow rate was increased to 500 sccm. The slurry feed rate and average residence time remained the same as in Experiment 1.

  Surprisingly, after stopping the experiment and filtering the liquid lignin conversion product, it was observed that the majority of the catalyst remained in the lignin conversion reactor (500). Finer particle catalyst was observed on the filter paper. Surprisingly, it was also observed that less catalyst was removed from the lignin conversion reactor when higher rates of lignin conversion were achieved, as evidenced by the lower amount of catalyst present on the filter paper. .

  It is conceivable that the sedimentation rate of the catalyst particles is larger than the removal rate of the lignin conversion product from the lignin conversion reactor (500) that is passed through the dip tube (610). This results in a surprisingly advantageous catalyst residence in the lignin conversion reactor. A fibrous Velcro®-like lignin-rich composition in a slurry containing lignin adheres itself to the catalyst particles (625) and removes them from the lignin conversion reactor, resulting in lower levels of lignin It is further conceivable that conversion is achieved. If it is desirable to remove all or part of the catalyst from the lignin conversion reactor, the diameter and length of the dip tube is reduced, thereby reducing the rate of removal of the lignin conversion product from the Parr reactor as a function of the catalyst settling rate. It is further contemplated that all or part of the catalyst can be removed from the Parr reactor by increasing to a level higher than the level.

Bubble column reactor Although the lignin conversion reactor can operate a process that is a continuous stirred tank reactor (CSTR), CSTR requires a large amount of energy input and to convert lignin on a continuous basis The required high pressure results in an unreasonably large reactor when utilizing CSTR. It has been discovered that bubble column reactors require smaller energy inputs and allow smaller reactors for continuous lignin conversion processes.

  One alternative to CSTR is the ebullated bed reactor described in US Pat. No. 4,240,644. One variation of the ebullated bed is a bubble column reactor. The bubble column reactor consists of at least one vertical cylinder that is at least partially filled with liquid. Gas is supplied through the gas supply pipe to the bottom of the cylindrical body, causing turbulence above the bubble flow. In a preferred embodiment, the gas can be hydrogen or nitrogen. In a preferred embodiment, the liquid can include water. In further embodiments, the liquid may include a hydrogen donor. The gas stream can be nitrogen or hydrogen gas at a rate sufficient to maintain the flow of catalyst particles within the liquid components of the reactor.

  In a preferred embodiment, the bubble column reactor also includes a gas distributor at the bottom of the vertical cylinder to allow for even distribution of bubbles. Preferred gas distributors include materials that are not corroded by the reactants, such as stainless steel mesh.

  The slurry containing lignin can be supplied to the bottom of a vertical cylinder through a slurry supply pipe. The amount of slurry containing lignin fed to the bubble column reactor achieves an increased rate of lignin conversion based on temperature, pressure, hydrogen flow, amount of catalyst and residence time, as described in the experimental section below. Can be changed as follows.

  In one embodiment, a plurality of catalysts can be charged to the bubble column reactor through a slurry feed tube. In another embodiment, multiple catalysts can be charged directly to the bubble column reactor and then a slurry containing hydrogen and / or lignin can be charged to the bubble column reactor.

  The reactor scheme for the bubble column also includes a second column for stripping solid unreacted lignin and catalyst and allowing it to flow by gravity into the bottom of the bubble column or boiling reactor and recontact with new gas. May be included.

  The bubble column reactor may also include a heating element that allows adjustment of the bubble column reactor temperature. Preferably, the heating element includes a plurality of heating coils wound around a vertical cylinder. In a preferred embodiment, the bubble column reactor temperature is 220 ° C to 350 ° C. Pressure and temperature reactor conditions should be selected to prevent carbide formation as described above.

  Bubble column reactor pressure can be varied based on bubble column reactor temperature and gas flow rate as described in the experimental section below. In a preferred embodiment, the bubble column reactor pressure is from 150 bar to 230 bar.

  A dip tube can be inserted at the top of the vertical cylinder to remove multiple lignin conversion products into the product receiver.

  In one embodiment, the bubble column reactor may consist of a plurality of vertical cylinders each having a separate gas supply tube, a separate slurry supply tube and a separate dip tube.

  It has been found that by utilizing a bubble column reactor instead of CSTR, a significant amount of energy savings can be achieved due to the lack of a separate stirring element. In addition, bubble columns convert slurries containing lignin into similar products while providing higher conversion than CSTR.

Bubble column reactor experiments Unless otherwise stated, the following procedure was applied to all experiments. Deionized water was added to the lignin-rich composition obtained from the pretreatment of lignocellulosic biomass to obtain a slurry containing lignin having a dry matter solids content of 5 weight percent of the mass of the slurry containing lignin. Insert the mixture into a blender (Waring blender, model HGBSS6) and mix thoroughly intermittently for 10 minutes at 30 second intervals (30 seconds of mixing then 30 seconds of mixing) to obtain a visually uniform slurry. (See experiment to establish the Waring HGBSS 6 blender's ability to disperse uniformly on a quantitative basis). The uniformity of the slurry containing lignin was evaluated with the naked eye.

  The slurry containing lignin was inserted into the mixing tank and stirring was continued. The mixing vessel was a stainless steel pan bottom vessel with a bottom outlet port connected to a Chandler Quizix QX dual syringe pump with two pump cavities. An inlet ball valve was inserted between the mixing tank and the two pump cavities of the Chandler Quizix QX dual syringe pump. The Chandler Quizix QX dual syringe pump is a gas distributor (1 inch inner diameter (1540), 30 inch height (1545), a heating element (1550), and a stainless steel mesh having a length of 2 inches ( 1570), a slurry feed tube (1560) at the bottom of the column having a length of 6 inches for feeding the lignin slurry to the bubble column reactor, and a bubble column reaction for taking the reaction product into the product receiver. Connected by flow (1510) to a bubble column reactor having a dip tube (1565) having a length of 8 inches connected to a transfer line (1580) at the top of the vessel. The product receiver was maintained at the same pressure as the bubble column reactor. The bubble column reactor further contained vents (1520) connected to the rupture disc (1521) and pressure transducer (1522). The bubble column reactor further contained a thermal well (1590) for measuring the temperature inside the bubble column reactor during the experiment.

  By opening and closing the inlet and outlet valves to allow the lignin slurry to flow continuously into the bubble column reactor, the slurry containing lignin is passed from the mixing vessel through a Chandler Quizix QX dual syringe pump. Flowed into the reactor.

  We performed a set of seven experiments. The results of these experiments are summarized in Table 3 and Table 4 below.

Bubble tower experiment 1
For experiment 1, 43 g of Raney nickel catalyst (1500) was charged directly into the bubble column reactor with 150 g of liquid water before the experiment was started. The system was continuously swept through the gas supply pipe (1530) and into the gas distributor (1570) at a gas flow rate of 300 scc / m. The bubble column reactor was heated to a bubble column reactor temperature of 310 ° C. to achieve a target bubble column reactor pressure of 165.5 bar. The slurry containing lignin was fed to the bubble column reactor at a rate of 3 mL / min. The slurry containing lignin was continuously fed to and removed from the bubble column reactor for a period of 5 hours or a total of 4.1 residence cycles of slurry containing lignin passing through the reactor. The total amount of slurry containing lignin flowing through the system was 45 g. When the inventors terminated the experiment, 11.1293 g of unreacted lignin-containing slurry remained in the bubble column reactor, but an unknown amount was taken out of the bubble column-containing slurry containing unreacted lignin. Leaked.

The lignin conversion product is G.I. C. In the composition measured by the mass spectrometer, it was observed that it was almost identical to the phenol oil produced during the lignin conversion process in a continuous stirred tank reactor (CSTR) (see FIG. 9). .
The conversion rate of the slurry containing lignin was 75.27% without taking into account the slurry containing an unknown amount of unreacted lignin that had flowed out.

Bubble tower experiment 2
For Experiment 2, we increased the bubble column reactor temperature from 310 ° C to 318 ° C. A certain amount of slurry containing lignin present in the bubble column reactor after reaching the assumed steady state during the experiment was 15.2587 g. All other conditions remained the same as in Experiment 1. When the inventors terminated the experiment, a slurry containing 15.2587 g of unreacted lignin remained in the bubble column reactor.

  It was observed that an increase in bubble column reactor temperature resulted in conversion of a slurry containing 66.09% lignin.

Bubble tower experiment 3
For Experiment 3, we reduced the amount of catalyst charged to the bubble column reactor from 43 g to 21.5 g. A certain amount of slurry containing lignin present in the bubble column reactor after reaching the assumed steady state during the experiment was 16.5924 g. All other conditions remained the same as in Experiment 2. When we terminated the experiment, a slurry containing 16.5924 g of unreacted lignin remained in the bubble column reactor.

  It was observed that the reduction of catalyst in the bubble column reactor resulted in a reduced conversion of the slurry containing 63.13% lignin.

Bubble tower experiment 4
For Experiment 4, we increased the bubble column reactor pressure from 166.49 bar to 172.4 bar and reduced the slurry flow rate from 3 mL / min to 2 mL / min. The total run time was increased to 6 hours and 40 minutes and the total charge of slurry containing lignin was reduced to 40 g. The number of turns of the slurry containing lignin through the bubble column reactor was reduced to 3.62. The total amount of slurry containing lignin present in the bubble column reactor after reaching the assumed steady state during the experiment was 18.4116 g. All other conditions remained the same as in Experiment 2. When we terminated the experiment, a slurry containing 18.4116 g of unreacted lignin remained in the bubble column reactor.

  It was observed that the reduction of the slurry flow resulted in a lower conversion of the slurry containing 53.97% lignin.

Bubble tower experiment 5
For Experiment 5, we further reduced the slurry flow rate from 2 mL / min to 1.2 mL / min. The total run time was increased to 10 hours and the total slurry charge containing lignin was reduced to 36 g. The residence cycle number of the slurry containing lignin through the reactor was reduced to 3.26. The total amount of slurry containing lignin present in the bubble column reactor after reaching the assumed steady state during the experiment was 14.2125 g. All other conditions remained the same as in Experiment 4. When we terminated the experiment, a slurry containing 14.2125 g of unreacted lignin remained in the bubble column reactor.

  At 4 hours, 8 hours, and 10 hours, the product receiver was depressurized and drained. After 4 hours, the product receiver contained 0.89 g of phenol oil. After 8 hours, the product receiver contained 3.25 g of phenol oil. After 10 hours, the product receiver contained 0.97 g of phenol oil. It was further observed that at the completion of the experiment, 2.4 g of phenol oil remained present in the transfer line. It was further observed that 1 g of phenol oil was present in the residual solid when the residual solid was drained from the bubble column reactor, filtered, washed with acetone, and rotoevaporated. A total of 8.51 g of phenol oil was recovered, resulting in a% phenol oil yield based on the amount of slurry containing 39.06% converted lignin. The phenol oil yield% based on the amount of slurry containing lignin charged to the bubble column reactor was 23.64%.

  Despite the reduction in slurry flow, it was observed that the increase in total run time resulted in higher conversion of the slurry containing 60.52% lignin.

Bubble tower experiment 6
For experiment 6, we increased the gas flow through the reactor from 300 scc / m to 600 scc / m resulting in a bubble column reactor pressure increase from 172.4 bar to 187.2 bar. Total run time was also increased to 12 hours. This resulted in an increased total input of slurry containing 72 g lignin. The number of residence cycles of the slurry containing lignin through the reactor was increased to 7. The total amount of slurry consisting of lignin present in the bubble column reactor at any one time during the experiment was 23.5214 g. All other conditions remained the same as in Experiment 4. When we terminated the experiment, a slurry containing 23.5214 g lignin remained in the bubble column reactor.

  At 2 hours 40 minutes, 5 hours 20 minutes, 8 hours, 10 hours 40 minutes and 12 hours, the product receiver was depressurized and drained. After 2 hours and 40 minutes, the product receiver contained 1.43 g of phenol oil. After 5 hours and 20 minutes, the product receiver contained 3.27 g of phenol oil. After 8 hours, the product receiver contained 2.64 g of phenol oil. After 10 hours and 40 minutes, the product receiver contained 4.7 g of phenol oil. After 12 hours, the product receiver contained 3.57 g of phenol oil. At the completion of the experiment, it was further observed that 9.29 g of phenol oil remained present in the transfer line. When the residual solid was drained from the bubble column reactor, filtered, washed with acetone, and rotoevaporated, it was further observed that 1.05 g of phenol oil was present in the residual solid. A total of 25.95 g of phenol oil was recovered, resulting in a phenol oil yield percentage based on the amount of slurry containing 53.53% converted lignin. The phenol oil yield% based on the amount of slurry containing lignin charged to the bubble column reactor was 36.04%.

  It was observed that the increase in gas flow rate resulted in a higher conversion of the slurry containing 67.33% lignin. It was further observed that the increase in gas flow rate increased the phenol oil yield ratio based on both the amount of slurry containing converted lignin and the amount of slurry containing lignin charged to the bubble column reactor.

Bubble tower experiment 7
For experiment 7, we increased the bubble column reactor temperature to 335 ° C. resulting in an increased bubble column reactor pressure of 207.9 bar. We also increased the amount of catalyst charged to the bubble column reactor to 85 g and the slurry flow rate from 2 mL / min to 3 mL / min. Total run time was reduced to 5 hours. This resulted in a reduced total input of slurry containing 45 g lignin. The residence cycle number of the slurry containing lignin through the reactor was reduced to 4.3. The total amount of slurry containing 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 we terminated the experiment, a slurry containing 12.082 g of lignin remained in the bubble column reactor.

  At 2 hours, 4 hours and 5 hours, the product receiver was depressurized and drained. After 2 hours, the product receiver contained 2.69 g of phenol oil. After 4 hours, the product receiver contained 1.34 g of phenol oil. After 5 hours, the product receiver contained 0.36 g of phenol oil. At the completion of the experiment, it was further observed that 11.92 g of phenol oil remained present in the transfer line. It was further observed that 1.25 g of phenol oil was present in the residual solid when the residual solid was drained from the bubble column reactor, filtered, washed with acetone, and rotoevaporated. A total of 17.56 g of phenol oil was recovered resulting in a% phenol oil yield based on the amount of converted lignin of 53.34%. The% phenol oil yield based on the amount of slurry containing lignin charged to the bubble column reactor was 39.02%.

  It was observed that the bubble column reactor temperature, the amount of catalyst and the increase in gas flow resulted in a higher conversion than any of the six experiments. Furthermore, the higher conversion rate does not result in a% increase in phenol oil yield based on the amount of lignin converted, but phenol oil based on the amount of slurry containing lignin charged to the bubble column reactor. It was observed to give an increase in yield.

^＊気泡塔反応器中のリグニンを含む総スラリーは、操作停止時に気泡塔反応器中で残留する未変換リグニンスラリーの量と等しい。BC1において、11.1293gの未変換リグニンが気泡塔反応器中で残留したが、実験終了時の気泡塔反応器からの取出時に不明量の未反応リグニンが流出し、不正確な計測値をもたらした。

^{* The} total slurry containing lignin in the bubble column reactor is equal to the amount of unconverted lignin slurry remaining in the bubble column reactor when operation is stopped. In BC1, 11.1293g of unconverted lignin remained in the bubble column reactor, but an unreacted amount of unreacted lignin flowed out upon removal from the bubble column reactor at the end of the experiment, resulting in inaccurate measurements. .

^＊11.1293gの未変換リグニンが反応器中で残留し、75.27%の実験BC1の変換率をもたらしたが、実験終了時の気泡塔反応器からの取出時に不明量の未反応リグニンが流出し、不正確な計測値をもたらした。

^* 11.1293 g of unconverted lignin remained in the reactor, resulting in a conversion rate of 75.27% of experimental BC1, but an unreacted amount of unreacted lignin was shed when removed from the bubble column reactor at the end of the experiment, Resulting in inaccurate readings.

  This lignin conversion process is considered a continuous process. This is because the lignin conversion product is removed from the lignin conversion reactor (500) in a continuous manner. The components of the slurry containing the reactants, for example lignin, are generally introduced into the lignin conversion reactor in a continuous manner as well. “Continuous mode” does not mean that the raw material or product is continuously introduced or removed at the same rate. For example, if only one piston pump is used, a slurry containing lignin is introduced into the lignin conversion reactor (500) in steady aliquots or pulses. Therefore, there is a period when there is no product flowing into the lignin conversion reactor. However, over time, the mass introduced into the lignin conversion reactor is equal to the mass removed from the lignin conversion reactor. One distinguishing feature between continuous and batch processes is that in the continuous process, the reactant feed is introduced into the lignin conversion reactor and / or the lignin conversion product is removed from the lignin conversion reactor. The reaction is carried out or progressed at the same time. Another approach to describe this is to perform conversion (eg, deoxygenation or hydrogenation) in a lignin conversion reactor while simultaneously or together withdrawing at least a portion of the lignin conversion product from the lignin conversion reactor. That is. Such extraction is performed in a continuous manner that includes pulse extraction.

  The process of the present invention converts lignin in the feed into several different product types. As described below, process conditions can be set to produce one class of compounds with a reduced amount of another class of compounds.

Lignin conversion can be regarded as dehydrogenation of lignin. Lignin does not convert to a single product, but to multiple lignin conversion products. The lignin-containing feed is exposed to additional hydrogen (H ₂ ) gas that can be added in a conventional manner depending on the temperature and pressure of the lignin conversion reactor. Multiple lignin conversion products may lack either ethylene glycol or propylene glycol.

  A first catalyst is also present in the lignin conversion reactor (500). The reason it is referred to as the first catalyst is that there may be a second catalyst added to the lignin conversion reactor, or the second catalyst is used to further react the lignin conversion product in different steps. Be able to. While there may be a second catalyst, in one embodiment, only one catalyst, the first catalyst, may be present. The lignin conversion reactor may lack a second catalyst.

  The lignin conversion product can include compounds found in jet fuel, or the lignin conversion product can be further converted to compounds including jet fuel.

  The first catalyst can be any one of the catalysts known to catalyze the reaction of hydrogen and lignin. The first catalyst used in the conversion process is preferably at least one produced by the Raney process described and claimed in US Pat. No. 1,628,190, the teachings of which are incorporated in its entirety. A sponge element metal catalyst containing a sponge element metal. The claimed method creates an alloy of at least a first metal and a second metal, dissolves the second metal from the first metal, and later produces a refined first elemental metal having a high surface area. leave. This high surface area is often described as a sponge structure. A preferred first catalyst for the lignin conversion process is known as Raney nickel, ie, the refined 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. Since water is a feature of the reaction, the catalyst structure, in particular its support, must be hydrothermally stable. Due to the heterogeneous nature, at least a portion of the first catalyst exists as a plurality of particles or in particle form. At least a portion of the first catalyst is not all of the first catalyst, but does not exist as a fixed bed.

  The first catalyst may or may not be supported and may or may not be supported, but generally does not exist as a fixed bed. When using a fixed bed catalyst, the feed should be present as a liquid as opposed to a slurry so that the solid does not plug the pores of the fixed bed. The idea of a fixed floor is part of the idea. This is because many of the feasible principles of this process are both slurry and liquid feeds that do not have solids, or at least less than 1% by weight where the solids are present in a size less than the pores of the fixed bed This is because it can be applied to a solid slurry.

  The amount of the first catalyst can be expressed by the weight of elemental nickel relative to the dry weight of the lignin feedstock, and the weight of elemental nickel relative to the dry weight of lignin in the feedstock ranges from about 0.25 to about 2.0. Within the range of about 0.3 to about 1.5, more preferably at least about 0.5 to 1.0. In one embodiment, the process lacks a catalytic amount of a second catalyst.

  The second catalyst, if used, can be any of the known standard hydrogenation catalysts, and the preferred second catalyst is the same as the first catalyst. When the second catalyst is the same as the first catalyst, the amount of the second catalyst is the same as the amount of the first catalyst. When deoxygenation and dehydrogenation are performed simultaneously in the same vessel, there is no additional second catalyst added as the first catalyst, the amount of which is the second for the purpose of the dehydrogenation reaction. Become a catalyst.

  There is also a preferred introduction of a third catalyst that is different from the first and second catalysts. A preferred third catalyst is a zeolite that creates a heterogeneous site for the reaction to proceed in an acidic environment.

Crystalline Metal Oxide Catalysts Sponge elemental metal catalysts made by the Raney process can be used in the present process, but they have many disadvantages. Sponge element metal catalysts made by the Raney method, such as Raney nickel, require extreme care before, during and after the reaction. Raney nickel is a particularly ignitable catalyst and must be maintained in an aqueous environment to avoid spontaneous combustion.

  In an alternative embodiment, the catalyst comprises a crystalline metal oxide catalyst. Crystalline metal oxide catalysts are not pyrophoric catalysts and can be handled at ambient conditions, unlike Raney nickel, which requires special handling conditions and storage in an aqueous environment.

  The crystalline metal oxide catalyst can be a crystalline single metal oxide catalyst or a crystalline binary metal oxide catalyst. In preferred embodiments, the crystalline metal oxide catalyst is in the form of nanoparticles having an average crystalline particle size of less than 250 nm, more preferably an average crystalline particle size of less than 150 nm, and an average crystalline particle size of less than 100 nm. Even more preferred, an average crystalline particle size of less than 50 nm is most preferred.

  When the catalyst is a crystalline single metal oxide catalyst, the metal can be selected from the group consisting of cesium, copper, nickel, iron, zinc and cobalt. One preferred crystalline single metal oxide catalyst is nickel oxide.

  In one embodiment, the crystalline metal oxide catalyst is a crystalline binary metal oxide catalyst. The crystalline binary metal oxide catalyst can be obtained from any of the known methods and methods that can be discovered in the future. In general, a crystalline single metal oxide catalyst, such as nickel oxide, is doped with atoms of a second metal, such as zinc, iron or cobalt. In this method, a portion of the metal species of the crystalline single metal oxide catalyst is replaced with a different metal species, resulting in a crystalline binary metal oxide catalyst. The crystalline single metal oxide catalyst can be doped with one or more metals. For example, a crystalline single metal oxide catalyst can be doped with zinc and iron metal oxides.

  When the catalyst is a crystalline binary metal oxide catalyst, the catalyst comprises at least two metals, at least one of which is platinum, palladium, cesium, copper, nickel, ruthenium, rhodium, gold, iron, cobalt And iridium. Preferred bimetallic oxide catalysts include bimetallic catalysts comprising nickel oxide doped with at least one element selected from the group consisting of zinc, iron and cobalt.

  In a preferred embodiment, 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 catalyst process.

  Preferably, the crystalline metal oxide catalyst converts lignin to a useful compound in a liquid solvent. In a preferred embodiment, the liquid solvent is water. In an alternative embodiment, 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 for functionalized phenols. Experiments were performed to demonstrate the ability of crystalline metal oxide catalysts to convert lignin to phenolic compounds.

Crystalline Metal Oxide Catalyst Experiment Pretreatment lignin feed stream and sufficient water from resources other than the pretreatment lignin feed stream to reach a 5 weight percent dry matter concentration in a 50 mL parr small reactor along with the catalyst. Inserted into. After the material was inserted into the reactor, the reactor was pressurized to about 15 bar with nitrogen, stirred for 5 minutes and vented.
The purging cycle was repeated two more times and then twice with hydrogen. Finally, the reactor was pressurized to 200 psi hydrogen pressure at 25 ° C. and then electrically heated to the reaction temperature. Once the internal temperature of the reactor was stabilized, the reactor was stirred for a reaction time of 60 minutes. When the reaction time was complete, the heating element was removed and the reactor was allowed to cool using an ice bath. Once the reactor had cooled to a temperature of 24 ° C., a gaseous sample was collected for further analysis and the reactor was vented until the pressure in the reactor was reduced to 0 psi.

  Nickel oxide nanoparticles were used as the catalyst. The average particle size of the nickel oxide catalyst particles can be obtained from the manufacturer Sigma-Aldrich Co. , LLC from St. Reported by Louis, Missouri, USA. In one experiment, nickel oxide nanoparticles were reduced to metallic nickel in hydrogen at 400 ° C. for 2 hours before charging the reactor. In other experiments, nickel oxide nanoparticles were not reduced in hydrogen prior to reactor charging.

  Upon completion of the reaction time and reactor cooling and venting, the reaction product was removed and analyzed to determine the amount of lignin converted and the yield of phenols in the conversion product. Conversion was determined by filtering the reaction mixture and extracting the filtered solution using dichloromethane. The residual organic layer was rotoevaporated and the residual solids ashed to determine the conversion rate of the process. The residual conversion product was sent to GC / MS analysis to determine the yield of phenols and the type of phenols produced.

Crystalline metal oxide experiment 1
For Experiment 1, we used nickel oxide reduced nanoparticles as the 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 make the slurry was deionized water. The reactor was heated to a reaction temperature of 305 ° C. and 0 hour was started. The reactor was further pressurized with hydrogen gas to a reaction pressure of 200 psi.

  At the end of the experiment, the reaction product profile showed that 83.0% of the lignin charged to the reactor was converted. This demonstrated that nickel oxide nanoparticles can be used as catalysts for lignin conversion.

Crystalline metal oxide experiment 2
For Experiment 2, we maintained all of the conditions of Experiment 1, except that 0.918 g of catalyst was charged to the reactor along with 2.5 g of lignin in the form of a lignin slurry.

  At the end of the experiment, the reaction product profile showed that 79.4% of the lignin charged to the reactor was converted. However, the yield of phenols based on converted 79.4% lignin was only 16.6%. This demonstrated that nickel oxide reduced nanoparticles can produce phenol oil, but not in high yield relative to the amount of conversion product. It should be noted here that only 55% of the pretreated lignin feed stream charged to the reactor contains lignin.

  GC / MS of the reaction product shows that the nickel oxide nanoparticles demonstrate a high selectivity for “light” phenols as opposed to “heavy”, which heavy and short chain hydrocarbons Defined as a molecule that has as a by-product.

Crystalline metal oxide experiment 3
For Experiment 3, we used nickel oxide unreduced nanoparticles. All other experiments remained the same as experiment 1.

  At the end of the experiment, the reaction product showed that 77.0% of the lignin charged to the reactor was converted. This demonstrated that nickel oxide unreduced nanoparticles convert lignin, but they do not convert as effectively as nickel oxide reduced nanoparticles.

Crystalline metal oxide experiment 4
For Experiment 4, we used nickel oxide unreduced nanoparticles. All other experiments remained the same as experiment 2.

  At the end of the experiment, the reaction product showed that 68.8% of the lignin charged to the reactor was converted. The reaction product also showed that 25.0% of the converted 68.8% lignin was converted to phenols. Again, it is important to note that only 55% of the pretreated lignin feed stream contains lignin. This is an 8.4% increase in yield compared to nickel oxide reduced nanoparticles. This means that nickel oxide unreduced nanoparticles cannot provide a similar conversion rate to nickel oxide reduced nanoparticles, whereas nickel oxide unreduced nanoparticles are a high percentage of the amount of lignin converted. It is demonstrated that it produces the phenols.

  GC / MS of the reaction product further shows that nickel oxide unreduced nanoparticles demonstrate similar selectivity to nickel oxide reduced nanoparticles over “light” phenol, avoiding heavys.

Crystalline metal oxide experiment 5
For Experiment 5, we reduced the amount of nickel oxide unreduced nanoparticles to 0.45 g. All other conditions remained the same as in Experiment 4.

  At the end of the experiment, the reaction product was converted to 61.8% of the lignin charged to the reactor, of which 23.3% were converted to phenols. Indicated. This demonstrates that reducing the amount of unreduced nanoparticles of nickel oxide can reduce the amount of lignin converted, but it does not significantly reduce the yield of phenols found in the converted lignin. .

Crystalline metal oxide experiment 6
For Experiment 6, we increased the reaction temperature from 305 ° C. to 315 ° C. and increased the amount of nickel oxide unreduced nanoparticles to 0.918 g. All other conditions remained the same as in Experiment 4.

  At the end of the experiment, 72.0% of the lignin charged to the reactor was converted at the end of the experiment, but only 79.4% of the lignin was converted to phenols. showed that. This demonstrates that while increasing the reaction temperature can increase the amount of lignin converted, it has an adverse effect on the yield of phenols found in the converted lignin.

Crystalline metal oxide experiment 7
For Experiment 7, we used methanol (MeOH) rather than distilled water as the solvent to make the lignin slurry. In addition, the inventors lowered the reaction temperature from 305 ° C. to 290 ° C. All other experiments remained the same as experiment 4.

  At the end of the experiment, the reaction product showed that 85.0% of the lignin charged to the reactor was converted. However, the final pressure in the reactor before cooling was significantly higher than in Experiment 4 (1508 psi and 251 psi). The GC / MS of the conversion product also showed that 13.0% of the conversion product was methane, differing from only 1.3% in Experiment 4.

  This means that methanol can be used as a solvent in this reaction, which can increase the amount of lignin that is converted, while it produces more methane than if distilled water was used as the solvent. Demonstrate that it also has harmful effects.

Crystalline metal oxide experiment 8
For Experiment 8, we used nickel oxide unreduced macrosize crystalline particles as a catalyst. All other experiments remained the same as experiment 4.

  At the end of the experiment, the reaction product showed that 75.7% of the lignin charged to the reactor was converted, but only 10.6% of the converted lignin was phenols. This demonstrates the need for nickel oxide nanoparticles rather than nickel oxide macroparticles when it is desired to convert lignin to phenols.

  The operating conditions and conversion rate data are reported in Table 5 below.

  As a further experiment, we obtained nickel oxide nanoparticles doped with other metal oxides (crystalline binary metal oxide catalysts). The average particle size is measured by the manufacturer Sigma-Aldrich Co. , LLC from St. Reported by Louis, Missouri, US. The operating conditions and conversion data for nickel oxide nanoparticles doped with other metals are reported in Table 6 below. Operating conditions and conversion data for Experiment 4 are included for comparison between nickel oxide nanoparticles doped with other metals and those not doped with other metals.

Crystalline metal oxide experiment 9
For Experiment 9, the inventors obtained nickel cobalt oxide nanopowder (Ni-CoO) number 634360-25G from Sigma-Aldrich. This catalyst had an average particle size of less than 150 nm. All other operating conditions remained the same as in Experiment 4.

  At the end of the experiment, the reaction product showed that 68.7% of the lignin was converted and that 23.2% of the converted lignin was phenols. The GC / MS of the reaction product further shows selectivity for “light” phenol as seen in Experiment 4. This means that between the nickel oxide nanoparticles and the nickel oxide nanoparticles doped with cobalt oxide, both in the conversion rate, in the yield of phenols, and in the type of phenols produced. Demonstrate that there is no significant difference.

Crystalline metal oxide experiment 10
For Experiment 10, the inventors obtained iron nickel oxide nanopowder (Fe—NiO), number 633149-25G, manufactured by Sigma-Aldrich. This catalyst had an average particle size of less than 50 nm. All other operating conditions remained the same as in Experiment 4.

  At the end of the experiment, the reaction product showed that 67.8% of the lignin was converted, but only 17.3% of the converted lignin was phenols. The GC / MS of the reaction product further shows selectivity for “light” phenol as seen in Experiment 4. This demonstrates that nickel oxide nanoparticles doped with iron oxide do not function as well as nickel oxide nanoparticles for the conversion of lignin to phenols.

Crystalline metal oxide experiment 11
For Experiment 11, the inventors obtained nickel zinc iron oxide nanopowder (Ni—Zn—FeO), number 641669-10G, manufactured by Sigma Aldrich. This catalyst had an average particle size of less than 100 nm. All other operating conditions remained the same as in Experiment 4.

  At the end of the experiment, the reaction product showed that 67.8% of the lignin was converted and surprisingly 37.2% of the converted lignin was phenols. The GC / MS of the reaction product further shows selectivity for “light” phenol as seen in Experiment 4. This demonstrates that nickel oxide nanoparticles doped with zinc and iron are highly desirable when it is desired to convert lignin to phenols.

Once the hydrogen donor solvent lignin feed stream has been converted to a converted lignin feed stream, the converted lignin feed stream can be further converted to an aromatic converted lignin product. A suitable converted lignin feed stream for this process comprises products derived from lignocellulosic biomass lignin. Typically, the product derived from lignocellulosic biomass lignin is phenol oil, a term used to describe a composition consisting of all of the phenols in the converted lignin feed stream. .

  The converted lignin feed stream is combined with one or more molecules. These hydrogen donor molecules are considered to be reactants, hydrogen donor molecules generated from the already converted lignin feed stream, hydrogens derived from resources other than the product stream from the already converted lignin feed stream. It can be selected from the group consisting of donor molecules and mixtures thereof.

The hydrogen donor molecule donates at least one hydrogen atom, all of which is consumed during the process. Examples of hydrogen donor molecules are compounds selected from the group consisting of aliphatic polyols having the formula H- [HC-OH] _n -H, where n is an integer from 2 to 10. This group includes sorbitol (n = 6), glycerol (n = 3), xylitol (n = 5) and ethylene glycol (n = 2). Thus, the hydrogen donor molecule can be selected from the group consisting of sorbitol, glycerol, xylitol and ethylene glycol.

  Another group of hydrogen donor molecules is

Wherein R ₁ is selected from the group consisting of —OCH ₂ , —H, and —OH, and R ₂ is —CH ₃ , —CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₃ and selected from the group consisting of —CH ₂ —CH ₂ —CH ₂ —CH ₃ ]
It is a molecule having

  Another group of hydrogen donor molecules is

Wherein 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. ]
It is a molecule having

  The hydrogen donor molecule is preferably not a molecule that produces an aldehyde as one of the final conversion products of the donation process. Terminal alcohols such as methanol and propanol molecules produce aldehydes as one of the final conversion products of the donation process. The hydrogen donor molecule preferably does not produce an aldehyde as one of the final conversion products of the donation process because the aldehyde creates a byproduct in subsequent processing.

  The hydrogen donor molecule can also be fed from a product stream from an already converted lignin feed stream, the product stream comprising cyclohexanol and substituted cyclohexanol. Hydrogen donor molecules selected from resources other than the product from the already converted lignin feed include isopropanol, ethylene glycol, glycerol, cyclohexanol and substituted cyclohexanol. In a more preferred embodiment, the hydrogen donor molecule is isopropanol. In an even more preferred embodiment, the plurality of hydrogen donor molecules is from cyclohexanol and substituted cyclohexanol from the products of the already converted lignin feed stream and from resources other than the products of the already converted lignin feed stream. Includes mixtures with cyclohexanol and substituted cyclohexanols. In the most preferred embodiment, the hydrogen donor molecules are cyclohexanol and substituted cyclohexanol derived from the converted lignin feed stream and separated therefrom during the early process. In one embodiment, the hydrogen donor molecule is further present with water.

  The required amount of hydrogen donor molecule or mixture thereof can be determined by the molar ratio between the number of moles of hydrogen donor molecule and the number of moles of phenol oil, and an average molecular weight of 150 g / mol is assigned to the phenol oil. The molar ratio of moles of hydrogen donor molecule to moles of phenol oil should preferably be in the range of 2.0: 1.0 to 10.0: 1.0, 3.0 : 1.0 to 9.0: 1.0 is more preferable, and 4.0: 1.0 to 8.0: 1.0 is even more preferable, and 5.0: 1.0 to 7. A range of 0: 1.0 is most preferred.

The role of H ₂ gas has been found to act as a detrimental substance for conversion to aromatic compounds. Therefore, the amount of H ₂ gas, when added to the reaction, should be kept below 25% of the total amount of hydrogen atoms [H] and H ₂ molecules used in the process and represents the following formula:

  The converted lignin feed stream and the hydrogen donor molecule are exposed to a metal catalyst, preferably a nickel-containing catalyst. Examples of nickel-containing catalysts are described herein and include heterogeneous Raney nickel catalysts as well as heterogeneous and homogeneous nickel oxide catalysts.

  The ratio of mmol of hydrogen donor molecule to mmol of catalyst metal is preferably in the range of 1.0: 1.0 to 5.0: 1.0, and 1.2: 1.0 to 4 A range of 0.0: 1.0 is more preferred, and a range of 1.5: 1.0 to 3.0: 1.0 is most preferred. Only the mmol of metal in the catalyst is used to calculate the mmol of the catalyst.

The materials are exposed to each other at reaction temperatures within the range of 190 ° C to 350 ° C, more preferably 200 ° C to 310 ° C, even more preferably 210 ° C to 300 ° C, most preferably 210 ° C to 280 ° C. The reaction time depends on the amount of catalyst by weight, the reaction temperature and the number of moles of hydrogen donor molecules (not H ₂ gas). Generally, this is in the range of 15 minutes to 6 hours, but a time of 10 minutes to 15 hours is envisaged.

  What has been discovered and demonstrated in the experimental part is that, when the reaction temperature is severe (> 190 ° C. or> 200 ° C.), the amount of aromatic reaction product is unexpectedly less than 5% from reactive organisms. , More than 30% reaction product, more preferably more than 40% reaction product, even more than 50% reaction product (more than 50% reaction product) Are most preferred.

  The process can be performed in both batch and continuous mode. In a continuous mode, the product is removed from the reaction vessel while causing the reaction. Where indicated, the examples were generated on a continuously stirred and heated reactor CSTR, but any reactor capable of removing the product from the reaction vessel while producing the reaction can be used for the continuous process.

Since lignin is often accompanied by difficult-to-process carbohydrates, it may be preferable to first treat the raw material with a carbohydrate conversion step. Fermentation is one such carbohydrate conversion step. Another carbohydrate conversion step, embodied in FIG. 1, creates a slurry lignin feedstock containing carbohydrates and lignin, which can be used in U.S. Patent Application Publication No. 2011-31487, US Patent Application Publication No. 2011-31488. The carbohydrate conversion reactor described in the specification and US Patent Application Publication No. 2011/0313212 is fed by pressurizing the slurry feed as described herein and feeding it into the first reaction zone. And
a) contacting the lignin slurry feedstock with hydrogen, water, catalyst in the first reaction zone in a continuous manner to produce an effluent stream comprising at least one polyol, hydrogen, water and at least one byproduct (hydrogen, Water and the raw material containing cellulose are flowing in a continuous manner, and the catalyst is
(I) Mo, W, V, Ni, Co, Fe, Ta, Nb, Ti, o, Zr and combinations thereof (the metal is in an elemental state, or the metal is a carbide compound, a nitride compound, or a phosphide compound) );
(Ii) Pt, Pd, Ru, and combinations thereof (the metal is in the elemental state) and (iii) essentially at least two selected from the group consisting of any combination of (i) and (ii) Consisting of active metal components);
b) separating hydrogen from the effluent stream and recycling at least a portion of the separated hydrogen to the reaction zone;
c) separating water from the effluent stream and recycling at least a portion of the separated water to the reaction zone;
d) recovering the polyol from the effluent stream or flowing the polyol with a plurality of hydrogen donor molecules.

  Depending on the catalyst selection and operation, this produces a mixture of polyols, such as ethylene glycol and propylene glycol, which can be used together as multiple hydrogen donor molecules.

Hydrogen Donor Experiment The following experiment establishes the ability of a hydrogen donor molecule to convert a converted lignin feed stream to a product containing a majority of the conversion compound as an aromatic compound called reformate.

The mmol of phenol oil is calculated as follows : The amount of phenol oil consists of all phenols (typically there are 5 different types of phenol units but with similar skeletal alkylphenol units). . Since phenol oil has an assigned average molecular weight of 150.0 g / mol used as a repeat unit when calculating the amount of mmol of phenol oil in the crude mixture, 5.0 g of phenol oil is 33. Has 3 mmol of phenols.

  The following data sets experimentally establish the ability of hydrogen transfer and / or hydrogen donor processes to produce highly aromatic streams with high selectivity over the prior art.

The experiments are arranged in three tables. Table 7a is a comprehensive characterization of the batch process operated on the feed stream derived as described above. The reaction conditions in the batch process were to use 2.0 mmol phenol oil per 1.0 g wet Raney Ni 2800 with a 1: 1 weight ratio of nickel to H ₂ O.

Table 7b is the overall characterization of the feed and the lower temperatures of the prior art shown in Table 7b. The reaction conditions according to the prior art were 0.2 g model phenolic compound feed and 1.0 g wet Raney Ni 2800 with a 1: 1 ratio of grams of nickel to grams of H ₂ O.

  In Table 8, the distribution and high yield of aromatic compounds are demonstrated. For example, when ethylene glycol was the hydrogen donor, aromatics accounted for 48.97% of the product out of the total amount of product in the reaction. In particular, when cyclohexanol was the donor, benzene was 15% of the aromatic compound.

  The process was extended to a continuous reaction under the following conditions.

Phenol oil conversion experiment with H donor solvent in CSTR CSTR1
H donor = isopropanol total reactor volume = 500 ml
Reactor volume used = 250 ml
Feed composition = 15 wt% phenol oil in isopropanol (14.0: 1.0 molar ratio H donor to phenol oil, MW = 148)
Reactor temperature = 230 ° C.
Reactor pressure = 68.95 bar
Nitrogen flow rate = 50 sccm
Stirrer speed = 600 rpm
Feed flow rate = 1.10 ml / min at 20 ° C = 2.10 ml / min at 230 ° C (density at 20 ° C = 0.787 g / ml, density at 230 ° C 0.412 g / ml)
Average residence time = 119 minutes Catalyst amount = 85 g wet Grace 2800 Raney Ni

Experiment CSTR2
H donor = isopropanol total reactor volume = 500 ml
Reactor volume used = 250 ml
Feed composition = 15 wt% phenol oil in isopropanol (14.0: 1.0 molar ratio H donor to phenol oil, MW = 148)
Reactor temperature = 250 ° C.
Reactor pressure = 89.63 bar
Nitrogen flow rate = 50 sccm
Stirrer speed = 600 rpm
Feed flow rate = 0.76 ml / min at 20 ° C = 2.10 ml / min at 250 ° C (density at 20 ° C = 0.787 g / ml, density at 250 ° C = 0.284 g / ml)
Average residence time = 119 minutes Catalyst amount = 85 g wet Grace 2800 Raney Ni

Experiment CSTR3
H donor = cyclohexanol total reactor volume = 500 ml
Reactor volume used = 250 ml
Feed composition = 10 wt% phenol oil in cyclohexanol (13.3: 1.0 molar ratio H donor to phenol oil, MW = 148)
Reactor temperature = 250 ° C.
Reactor pressure = 68.95 bar
Nitrogen flow rate = 100 sccm
Stirrer speed = 600 rpm
Feed flow rate = 2.00 ml / min at 20 ° C. = 2.66 ml / min at 250 ° C. (density at 20 ° C. = 0.951 g / ml, density at 250 ° C. = 0.715 g / ml)
Average residence time = 94 minutes Catalyst amount = 50 g wet Grace 2800 Raney Ni

Experiment CSTR4
H donor = cyclohexanol total reactor volume = 500 ml
Reactor volume used = 250 ml
Feed composition = 10 wt% phenol oil in cyclohexanol (13.3: 1.0 molar ratio H donor to phenol oil, MW = 148)
Reactor temperature = 280 ° C.
Reactor pressure = 68.95 bar
Nitrogen flow rate = 100 sccm
Stirrer speed = 600 rpm
Feed flow rate = 1.80 ml / min at 20 ° C. = 2.54 ml / min at 280 ° C. (density at 20 ° C. = 0.951 g / ml, density at 280 ° C. = 0.673 g / ml)
Average residence time = 98 minutes Catalyst amount = 50 g wet Grace 2800 Raney Ni

Experiment CSTR5
H donor = 4-methylcyclohexanol total reactor volume = 500 ml
Reactor volume used = 250 ml
Feed composition = 9 wt% phenol oil in 4-methylcyclohexanol (13.1: 1.0 molar ratio H donor to phenol oil, MW = 148)
Reactor temperature = 250 ° C.
Reactor pressure = 68.95 bar
Nitrogen flow rate = 400 sccm
Stirrer speed = 600 rpm
Feed flow rate = 1.90 ml / min at 20 ° C = 2.50 ml / min at 250 ° C (density at 20 ° C = 0.913 g / ml, density at 250 ° C = 0.693 g / ml)
Average residence time = 100 minutes Catalyst amount = 50 g wet Grace 2800 Raney Ni

Experiment CSTR6
H donor = 4-methylcyclohexanol total reactor volume = 500 ml
Reactor volume used = 250 ml
Feed composition = 9 wt% phenol oil in 4-methylcyclohexanol (13.1: 1.0 molar ratio H donor to phenol oil, MW = 148)
Reactor temperature = 280 ° C.
Reactor pressure = 68.95 bar
Nitrogen flow rate = 100 sccm
Stirrer speed = 600 rpm
Feed flow rate = 1.70 ml / min at 20 ° C = 2.37 ml / min at 280 ° C (density at 20 ° C = 0.913 g / ml, density at 280 ° C = 0.654 g / ml)
Average residence time = 105 minutes Catalyst amount = 50 g wet Grace 2800 Raney Ni

  Table 9 shows the differences between the batch process and the CSTR reaction process.

High catalyst ratio While previous experiments were performed using a low catalyst to feed ratio, the inventors performed additional experiments where excess catalyst was added to the reactor. It has been discovered that when a high catalyst to feed ratio is used, the reaction produces more aromatic compounds than a low catalyst to feed ratio.

  When converting lignin to an aromatic compound, the ratio of moles of catalyst to moles of lignin is preferably greater than 4: 1 and more preferably the ratio of moles of catalyst to moles of lignin is greater than 5: 1. Even more preferably, the ratio of moles of catalyst to moles of lignin is greater than 6: 1. Preferably, the ratio of moles of catalyst to moles of lignin ranges between 4: 1 and 15: 1 and the ratio of moles of catalyst to moles of lignin is between 4: 1 and 12: 1. And more preferably, the ratio of moles of catalyst to moles of lignin is between 4: 1 and 10: 1, and the ratio of moles of catalyst to moles of lignin is from 4: 1. A range between 9: 1 is even more preferred, and a ratio of moles of catalyst to moles of lignin between 5: 1 and 9: 1 is even more preferred.

The ratio of catalyst to lignin can also be expressed as the ratio of mmol of catalyst to mmol of lignin multiplied by the total active catalyst surface area (m ² ):
mmol (catalyst) x total active surface area (catalyst) / mmol (lignin)

Once the total active surface area per mmol of catalyst used is known, it is possible to easily calculate the total active catalyst area (m ² ). For example, Raney nickel catalysts are known to have an active surface area between 10.5 m ² / mmol Ni and 13.1 m ² / mmol Ni. By specifying an active surface area of 11.8 m ² / mmol for the Raney nickel catalyst, the effective active catalyst total surface area can be easily calculated. For example, when 38.4 mmol of Raney nickel catalyst is used, the effective active catalyst has a total surface area of 453 m ² . The ratio of mmol of catalyst to mmol of lignin multiplied by the total active catalyst surface area is preferably in the range between 4900: 1 and 15000: 1, more preferably in the range between 6500: 1 and 14000: 1. Even more preferred is a range between 8000: 1 and 13000: 1.

  In the case of a mixed catalyst, the formula is the sum of mmoles of all catalysts, and the surface area is the surface area of the solid particles containing the catalyst (s).

  In the case of a catalyst on a support, the surface area is that of a solid with the catalyst on the support.

  The area is not just the area of the catalytic metal, but the surface area of the solid particles containing the catalyst (s).

  By converting lignin directly to aromatics, the process is considered a deoxygenation process. Preferably, the deoxygenation process occurs at deoxygenation temperature and deoxygenation pressure during the deoxygenation time.

  Preferably, the deoxygenation temperature is in the range between 205 ° C and 325 ° C, more preferred is a deoxygenation temperature in the range of 215 ° C to 300 ° C, and a deoxygenation temperature in the range of between 225 ° C and 280 ° C. Is even more preferred.

  Preferably, the deoxygenation pressure is in the range between 60 bar and 100 bar, more preferably the deoxygenation pressure is in the range between 70 bar and 100 bar, and the deoxygenation pressure in the range between 75 bar and 95 bar is most preferred. preferable.

  The inventors conducted experiments to evaluate the ability of the high catalyst to raw material ratio to convert the raw material to an aromatic compound. The results of these experiments are summarized in Table 10 below. Each experiment was performed using a Parr 4575 reactor. In each experiment, 5 grams of wet lignin was combined with deionized water and charged with various amounts of Johnson Matthey A-5000 sponge nickel catalyst. The reactor was pressurized with hydrogen gas at 25 ° C. to a pressure between 2.5 and 6 bar. The reactor was heated to the reaction temperature and stirred for the reaction time. The final operating pressure varied between 75 bar and 95 bar. When the reaction was complete, the reactor was cooled and the reaction product was filtered and analyzed using GC / MS.

  In the present description and claims, the number of moles of catalyst is calculated as the number of moles of active nickel in the catalyst. The Johnson Matthey A-5000 sponge nickel catalyst contains approximately 50% water and 50% metal, approximately 90% of the metal is reactive nickel, while the remaining 10% is non-reactive aluminum. As an example, 0.6 g of catalyst contains 0.3 g of metal, nickel is 0.27 g, or the active nickel of the catalyst is 4.6 mmol.

  In the present description and claims, the moles of lignin are calculated based on the assigned molecular weight of 180 g / mol (which is based on the assumed molecular weight of the repeat unit). As an example, 5 g wet lignin contains 50% water and 50% lignin, yielding 2.5 g lignin or 13.9 mmol lignin.

The results of these experiments show that when a higher catalyst ratio relative to the amount of lignin is loaded into the reaction, the reaction will have a higher concentration of aromatic product than the aromatic product found at the lower catalyst to lignin ratio. To produce. The relationship between the ratio of catalyst to lignin and the amount of aromatics produced appears to be linear with the amount of aromatics produced, with a catalyst to lignin ratio of about 7.2: 1. The maximum is approximately 80%. Considering that the catalyst used in these experiments is Raney nickel with an assigned surface area of 11.8 m ² / mmol, this is the number of moles of catalyst multiplied by the total active catalyst surface area (m ² ). It corresponds to the ratio of moles of lignin, 12732: 1 For example, Comparative Example 1 (Experiment No. CE1) 0.6 grams of catalyst was used for 5 grams of wet lignin. The reaction product showed only 3.5% aromatic product. As a control, in high amount catalyst 3 (experiment number HC3), 16 g catalyst was used for 5 g wet lignin. The reaction product showed 79.42% aromatic product.

  As discussed herein, a carbohydrate conversion process can be performed that provides lignocellulosic biomass prior to the above process.

  The above process can use raw materials from commercially available lignocellulosic ethanol plants, but is flexible enough to use lignin-containing raw materials from other processes at the same time. After the majority of the carbohydrate fraction has been biologically converted to ethanol, the current feed comes from naturally occurring lignocellulosic biomass. The sulfur content of the feed is nearly zero, and consequently desulfurization is not required to obtain jet fuel (in contrast to fossil feed).

  In most second generation biofuel processes, lignin by-products are recovered after distillation and used as boiler fuel to produce steam and electricity. This is not necessarily the best use of those lignin-rich residues (LRR).

  The envisaged process uses at least the above process if the biorefinery produces ethanol (or some other product) from the carbohydrate fraction of lignocellulosic biomass while others do not utilize it for lignin conversion LRR is used as a raw material for fuels and chemicals produced in this way.

  For example, the ethylene glycol used in the hydrogen donor solvent process is derived from the conversion of carbohydrates to ethylene glycol as described in the art. Other alcohols are also well known. Carbohydrate conversion can be catalytic or enzymatic. Since the lignin conversion process does not use a pure hydrogen donor, it is not necessary to purify carbohydrate conversion products, such as ethylene glycol.

  The plurality of conversion products preferably comprises at least one product selected from the group consisting of carbon dioxide, methane, ethane, phenols, benzene, toluene, and xylene.

  It should be clear from FIG. 4 how the reaction process can be operated as a CSTR (continuous stirred tank reactor).

  The present invention taught by in-situ separation using a dip tube is applicable to almost any solid-liquid where the solid is present as finely dispersed particles. This aspect of the invention is not limited to the lignin conversion process.

  Another embodiment of the process cools a plurality of lignin conversion products after exiting the reactor that separates the vapor from the liquid and solid, and the back pressure regulator (700) after the solid-liquid separator (600). It is possible to control the pressure of the lignin conversion process.

  The temperature of the lignin conversion product produced by the lignin conversion process is substantially higher than the temperature of the pretreatment steam, soaking and fermentation processes and the carbohydrate conversion process preceding the lignin conversion process. We specifically contemplate transferring heat from the lignin conversion product to the pretreatment process soaking, steam pretreatment, hydrolysis, and / or fermentation process in an integrated or co-located operation.

  Once these liquid lignin conversion products are obtained, they can then be subsequently converted to a number of different chemical raw materials 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 into polyester and subsequent articles, such as soft drink bottles, beer bottles, and other packaging articles, can be done using conventional techniques known today and techniques that can be invented in the future. Can be achieved.

  Since lignin is often accompanied by carbohydrates that are difficult to process, it may be preferable to first treat the raw material through a carbohydrate conversion step to obtain a carbohydrate conversion product. In a preferred embodiment, the carbohydrate conversion product is selected from the group consisting of alcohol, polyol, glucan, gluco-lignin and cellulose.

Fermentation is one such carbohydrate conversion step. Another carbohydrate conversion step, embodied in FIG. 1, creates a slurry feedstock containing carbohydrates and lignin, which is incorporated by reference in US 2011/31487 and US 2011/31488. And the carbohydrate conversion reactor described in US 2011/0313212 by pressurizing the slurry feed as described herein and feeding it into the first reaction zone. ,
a) contacting the lignin slurry feedstock in a continuous manner with hydrogen, water, and catalyst in a first reaction zone to produce an effluent stream comprising at least one polyol, hydrogen, water and at least one byproduct (hydrogen The feedstock, including water and cellulose, is flowing in a continuous manner, and the catalyst in the first reaction zone is
(I) Mo, W, V, Ni, Co, Fe, Ta, Nb, Ti, o, Zr and combinations thereof (the metal is in an elemental state, or the metal is a carbide compound, a nitride compound, or a phosphide compound) );
(Ii) Pt, Pd, Ru, and combinations thereof (the metal is in the elemental state) and (iii) essentially at least two selected from the group consisting of any combination of (i) and (ii) Consisting of active metal components);
b) separating hydrogen from the effluent stream and recycling at least a portion of the separated hydrogen to the reaction zone;
c) separating water from the effluent stream and recycling at least a portion of the separated water to the reaction zone;
d) recovering the polyol from the effluent stream.

  After recovering a carbohydrate converted from the effluent stream, such as a polyol, to create a secondary feed stream containing lignin, the secondary feed stream containing lignin is optionally re-pressurized and a lignin conversion reactor ( 500) to convert lignin into phenols and other components of the plurality of lignin conversion products.

  In a preferred embodiment, polyols such as ethylene glycol and propylene glycol can be used as hydrogen donors to convert lignin to lignin conversion products. In another embodiment, hydrogen from the effluent stream can be used as a hydrogen source to convert lignin to a lignin conversion product. Also, the water from the effluent stream can be recycled or reused as treated water for pretreating the lignocellulosic biomass feedstock.

  Having described the fundamental operation, reference can be made to FIG. 1, which describes one embodiment and variations thereof. As shown in FIG. 1, the conversion of lignocellulosic biomass can begin with either pretreated lignocellulosic biomass (20A or 20B) or untreated lignocellulosic biomass (10A or 10B). Stream A is fed during an optional carbohydrate conversion process to convert carbohydrates to useful products before converting lignin. The selected feed enters the carbohydrate conversion reactor (100) via stream (110). Additional reactants, such as hydrogen, are added into (120). When lignocellulosic biomass is added as a slurry and a catalyst is used, the described handling principle of creating a continuous process applies, as well as reducing the implementation of this process. After the conversion, the carbohydrate conversion product is flowed from the carbohydrate conversion reactor (100) to the carbohydrate conversion product recovery unit (200) via the flow (210). There can be two types of carbohydrate conversion products, one is a gas that flows out via (220). This gas can be methane, which can be converted to hydrogen by known techniques such as steam reforming. Hydrogen is used to convert either more carbohydrates or lignin by introducing hydrogen through stream (520) into lignin conversion reactor (500). When an embodiment produces ethylene glycol, the ethylene glycol is transferred to a polyester manufacturing facility via stream (230), which converts the ethylene glycol into a polyester resin that is later converted into a final polyester article, such as a preform and Convert to a polyester bottle.

  Lignin from the carbohydrate conversion process flows via stream (310) into the lignin slurry creation step (300). Embodiments without the first carbohydrate conversion step are indicated by streams (20B) and (10B), respectively. As contemplated by the inventors, they could be fed directly and proved to be continuously converted when fed directly during the slurry making step (300). Make-up water or other solvent is added via stream (320) and an optional vacuum is applied through stream (330).

  If the lignocellulosic feedstock of either (20B) or (10B) is already in slurry form, step (300) can be omitted and stream (10B) or (20B) can be sent to one or more slurry pumps ( 400) directly through stream (410). The pumping system described above increases the pressure of the slurry until it exceeds the reactor conversion pressure of the lignin conversion reactor (500). After pressurizing the slurry until the reactor conversion pressure of the lignin conversion reactor is exceeded, the slurry pump passes the slurry containing lignin through the outlet valve (450) through the stream (510) to the lignin conversion reactor (500). To discharge. The lignin conversion reactor (500) contains a lignin slurry and at least a first catalyst. Hydrogen enters the lignin conversion reactor (500) at a pressure through stream (520). As CSTR, the lignin conversion product is passed through the dip tube (610) and the catalyst settles again in the lignin conversion reactor (500). The vessel (600) is a solid-liquid separator, and gas by-products flow out of the separation vessel (600) via a flow (710) and flow in a back pressure regulator (700) that controls the pressure of the entire system. . After depressurization, gas is passed through stream (720). After the carbohydrate was introduced into the lignin conversion reactor, stream (720) contained the methane conversion product of the carbohydrate, and thus the carbohydrate conversion process was performed in situ with the lignin conversion. Methane can be further converted to hydrogen, for example via steam reforming, and reused in the process, thus making the process at least partially self-contained for hydrogen.

  The solid from the lignin conversion process is separated from the liquid in step (600), the solid flows in stream (620), and the liquid flows through stream (810) to BTX conversion step (800). The stream (650) in FIG. 3 shows the separation of water from the lignin conversion process. While water is present in the liquid phase, some water vapor may also be present in (720). As shown in FIG. 1, in this embodiment, at least a portion of the water is reused to create or supplement a slurry containing lignin. Since the lignin conversion process is the final water generator, some water is purged in the stream (620).

  The conversion of phenols to BTX is a well-known chemical reaction and several routes are available. Since the lignin conversion process mainly produces phenols, the conversion of phenols by known routes is considered well within the skill of those skilled in the art. Once BTX (benzene, toluene, xylene) is formed, it is passed through a conversion step to convert BTX to terephthalic acid, reacting terephthalic acid with ethylene glycol, a polyester resin and subsequently an article from the polyester resin (900) Can be made via the flow (910). It is also sufficient to convert these products to terephthalic acid and react terephthalic acid with ethylene glycol to make polyester resins and subsequently articles from polyester resins, such as films, trays, preforms, bottles and jars. Are within the skill of those skilled in the art.

Integrated process experiment
The material preparation experiment used a composition obtained from wheat straw as a starting material.

  The raw material was subjected to an immersion treatment in water at a temperature of 155 ° C. for 65 minutes, and then steam exploded for 4 minutes at a temperature of 190 ° C.

  The steam-exploded material and the liquid from the soaking material were mixed together and subjected to enzymatic hydrolysis, fermentation to ethanol and distillation.

  The detailed parameters used are considered unrelated to the experiment if the content of the composition is preserved.

  The liquid and solid mixture after distillation was pressed at 15 bar and 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.

  The lignin-rich composition was subjected to a temperature lower than 0 ° C. and kept frozen until the experiment was performed.

Lignin Conversion Procedure Unless otherwise stated, the following procedure was applied to all experiments that did not use a bubble column.

  The composition containing high content of frozen lignin was naturally thawed until a temperature of 20 ° C. was reached.

  Deionized water was added to the lignin-rich composition to reach the final lignin-rich composition concentration in the slurry designed in each experiment. The mixture was inserted into a blender (Waring blender, model HGBSS6) and mixed intermittently (eg, 30 seconds pulsed on, 30 seconds off) for 10 minutes to obtain a uniform slurry. The uniformity of the slurry was evaluated with the naked eye.

  The slurry was inserted into the mixing tank and stirring was continued. The mixing tank was a stainless steel dish bottom tank with a bottom discharge port connected to a Chandler Quizix QX dual syringe pump with a full port ball valve connected to a lignin conversion reactor. The pump discharge was connected to the reactor by a tube.

  The lignin conversion reactor was a Parr 4575 reactor with two 45 ° inclined turbine blades, cooling coils, separate gas and slurry feed ports, and a discharge dip tube. The reactor was charged with water (about 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 shown as the ratio of the weight of catalyst to the weight of dry matter of the lignin-rich composition added to the lignin conversion reactor in one residence time. Hydrogen was inserted into the lignin conversion reactor at a temperature of 20 ° C. 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 a continuous flow of hydrogen was started into the lignin conversion reactor. The lignin conversion reactor was connected to a product receiver maintained at 25 ° C. The pressure was measured by a pressure transducer (Ashcroft Type 62) connected to the lignin conversion reactor and controlled by a back pressure regulator (Dressor Mite 5000, model 91) located downstream of the product receiver. The temperature was increased to the reaction temperature and a slurry stream containing lignin was introduced into the lignin conversion reactor. The slurry flow rate was calculated to obtain the residence time of the lignin feed in the reactor in each experiment at operating conditions. After a time corresponding to three residence times, steady-state conditions were considered reached and solid and liquid reaction products were collected in the receiver for a time corresponding to one residence time. The receiver was depressurized to atmospheric pressure, the non-gaseous reaction product was extracted with methyl tert-butyl ether organic solvent, filtered, and the liquid phase was separated by a separatory funnel.

  This system was operated continuously for a maximum of 2 shifts (about 16 hours) without stopping the operation.

  Experiments were performed according to the described procedure. Experimental parameters are reported in Table 12.

  The experiment produced the following main products:

Wastewater Treatment Recycling The lignin conversion process of catalytic hydrogenation has also been found to remove most of the contaminants from the stillage water entering the process.

  This is facilitated by analyzing the chemical oxygen demand, also known as stillage COD from the fermentation prior to the lignin conversion process (carbohydrate conversion process), and then analyzing the COD from the aqueous phase after the lignin conversion process. Proven in

  According to observation, the untreated stillage in the glass sample container appeared as a dark brown homogeneous solution. Prior to processing in the lignin conversion process, the liquid fraction was dark brown to black and showed large amounts of soluble contaminants. After flowing water through the lignin conversion process (as part of the lignocellulosic biomass feedstock), the water was separated from the organic product. The water was no longer dark, but amber and pale gold.

  When measured for COD, the untreated stillage was a COD of 54,000 mg / L. The COD of the treated water during the lignin conversion process was 17,000 mg / L and the COD was reduced by 69%.

  Thus, one embodiment of the process preferably produces an aqueous phase having a COD concentration of less than 50% of the COD concentration of the aqueous phase of the lignin feedstock of the lignin conversion process. Less than 40% is more preferred and less than 32% is most preferred.

  The aqueous phase may be recycled or reused in the carbohydrate conversion step as immersion water, steam explosion water or other wash water or fermentation stream with or without further COD removal or COD concentration reduction. Or it can be reused or recycled in the lignin conversion step as part of slurry production or makeup water.

  Reuse or recycling of just 10% of the aqueous phase has important implications for wastewater treatment, which is a significant part of the cost of operating a carbohydrate conversion process, lignin conversion process, or integration process.

  Prior to processing in the lignin conversion process, water from the lignocellulosic feed was removed for visual and analytical evaluation.

  This reuse of water is illustrated in FIG. 3, where at least a portion of the water from the reaction is separated from the lignin conversion product and reused in the process. Water shown as stream (650) may be used in the slurry in stream (320), or as part of a hydrolysis step in (120) of carbohydrate conversion, or used in a pretreatment soaking or steam explosion step. it can. If water is not reused, it is generally sent to wastewater treatment for further purification and reintroduction into the environment.

Analytical measurement
1. Composition of lignin-rich composition The composition of the lignin-rich composition was measured according to the following standard procedure.

Determination of Structural Carbohydrates and Lignin in Biomass
Laboratory Analytical Procedure (LAP) issue date: 4/25/2008
Technical Report NREL / TP-510-42618 Revised April 2008

Determination of Extractives in Biomass
Laboratory Analytical Procedure (LAP) Date: 7/17/2005
Technical Report NREL / TP-510-42619 January 2008

Preparation of Samples for Compositional Analysis
Laboratory Analytical Procedure (LAP) Date: 9/28/2005
Technical Report NREL / TP-510-42620 January 2008

Determination of Total Solids in Biomass and Total Dissolved Solids in Liquid Process Samples
Laboratory Analytical Procedure (LAP) issue date: 3/31/2008
Technical Report NREL / TP-510-42621 March Revised March 2008

Determination of Ash in Biomass
Laboratory Analytical Procedure (LAP) Date: 7/17/2005
Technical Report NREL / TP-510-42622 January 2008

Determination of Sugars, By Products, and Degradation Products in Liquid Fraction Process Samples
Laboratory Analytical Procedure (LAP) issue date: 12/08/2006
Technical Report NREL / TP-510-42623 January 2008

Determination of Insoluble Solids in Pre-prepared Biomass Material
Laboratory Analytical Procedure (LAP) Date: 03/21/2008
NREL / TP-510-42627 March 2008

2. Liquid Product Composition The composition of the liquid product was measured with an Agilent 7890 gas chromatogram and Agilent 5975C mass detector according to the following procedure and parameters.

Injector parameters in the gas chromatogram:
Injection volume: 2ul
Pulsed split injection Injection pulsed pressure: 50 psi, 0.5 min temperature: 220 ° C
Pressure: 20.386 psi
Septum purge: 3 ml / min Split ratio: 10: 1
Split flow 13ml / min

Analytical column:
Column: Restek RXI-5Sil MS, 30 meters, inner diameter 0.25 mm, film thickness 0.5 um
Flow (He): 1.3 ml / min

MSD transfer pipeline: (mass detector)
Temperature profile: 280 ° C for the entire run
Column transfer line: HP-101 methylsiloxane-101 methylsiloxane: 12 m × 200 μm × 0.25 μm

Oven parameters: (connected to column)
40 ° C, 1 minute to 220 ° C, 12 ° C / minute, 0 minute to 300 ° C, 30 ° C / minute, 17 minutes

Detector parameters:
Temperature: 310 ° C
H ₂ flow: 45 ml / min Air flow: 450 ml / min Supply flow: 26.730 ml / min

MS acquisition parameters:
EM voltage: 1871
Low mass: 10
High mass: 350.00
Threshold value: 25
Number of samples: 3
MS source: 230 ° C
MS quadrupole: 150 ° C
The relevant content relative to the weight of the product and liquid product was identified by NIST2008 peak identification software. Only products corresponding to areas greater than 1% of the total spectral area are reported.

3. Solid product composition The filtered solid was dried and then incinerated. The burning part was regarded as unreacted lignin. The ash portion was considered a nickel catalyst.

4). The composition of the gaseous product was identified by gas chromatography.

Claims (16)

A method for conversion of a converted lignin biomass feed stream into a converted lignin stream, the method comprising:
A) combining lignin and at least a first solvent with a first catalyst in a reaction vessel, wherein the ratio of moles of first catalyst to moles of lignin is between 4: 1 and 15: 1. Step B) comprising deoxygenating the lignin biomass feed stream to a converted lignin stream at a deoxygenation temperature and a deoxygenation pressure during the time of deoxygenation.
Said method.   The process of claim 1 wherein the ratio of moles of first catalyst to moles of lignin ranges between 4: 1 and 12: 1.   The process of claim 1 wherein the ratio of moles of first catalyst to moles of lignin ranges between 4: 1 and 10: 1.   The process of claim 1, wherein the ratio of moles of first catalyst to moles of lignin ranges between 4: 1 and 9: 1.   The process of claim 1 wherein the ratio of moles of first catalyst to moles of lignin ranges between 5: 1 and 9: 1.   The method according to any one of claims 1 to 5, wherein the deoxygenation temperature is in a range between 205C and 325C.   The method according to any one of claims 1 to 5, wherein the deoxygenation temperature is in a range between 215 ° C and 300 ° C.   The method according to any one of claims 1 to 5, wherein the deoxygenation temperature is in a range between 225 ° C and 280 ° C.   9. The first catalyst according to any one of claims 1 to 8, wherein the first catalyst comprises a metal catalyst, the metal being selected from the group consisting of nickel, palladium, platinum, ruthenium, rhodium, molybdenum, cobalt and iron. Method.   10. A method according to any one of the preceding claims, wherein the deoxygenation pressure is in the range between 60 bar and 100 bar.   10. A method according to any one of the preceding claims, wherein the deoxygenation pressure is in the range between 70 and 100 bar.   10. A method according to any one of the preceding claims, wherein the deoxygenation pressure is in the range between 75 bar and 95 bar.   13. A method according to any one of the preceding claims, wherein the deoxygenation time is in the range between 5 minutes and 2 hours.   13. A method according to any one of the preceding claims, wherein the deoxygenation time is in the range between 10 minutes and 1.5 hours.   13. A method according to any one of the preceding claims, wherein the deoxygenation time is in the range between 15 minutes and 1 hour.   The method according to any one of claims 1 to 15, wherein the reaction vessel is an ebullated bed reactor.

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