Lignosulfonates

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Lignosulfonates (LS) are water-soluble anionic polyelectrolyte polymers: they are byproducts from the production of wood pulp using sulfite pulping. [1] Most delignification in sulfite pulping involves acidic cleavage of ether bonds, which connect many of the constituents of lignin. [2] Sulfonated lignin (SL) refers to other forms of lignin by-product, such as those derived from the much more popular Kraft process, that have been processed to add sulfonic acid groups. The two have similar uses and are commonly confused with each other, with SL being much cheaper. [3] LS and SL both appear as free-flowing powders; the former is light brown while the latter is dark brown. [1]

Contents

Lignosulfonates have very broad ranges of molecular mass (they are very polydisperse). A range of from 1,000 to 140,000 Da has been reported for softwood lignosulfonates with lower values reported for hardwoods. Sulfonated Kraft lignin tends to have smaller molecules at 2,000–3,000 Da. [1] SL and LS are non-toxic, non-corrosive, and biodegradable. A range of further modifications may be applied to LS and SL, including oxidation, hydroxymethylation, sulfomethylation, and a combination thereof. [3]

Preparation

Lignosulfonates

Lignosulfonates are recovered from the spent pulping liquids (red or brown liquor) from sulfite pulping. Ultrafiltration can also be used to separate lignosulfonates from the spent pulping liquid. [1] A list of CAS numbers for the various metal salts of lignosulfonate is available. [4]

The electrophilic carbocations produced during ether cleavage react with bisulfite ions (HSO3) to give sulfonates.

R-O-R' + H+ → R+ + R'OH
R+ + HSO3 → R-SO3H

The primary site for ether cleavage is the α-carbon (carbon atom attached to the aromatic ring) of the propyl (linear three carbon) side chain. The following structures do not specify the structure since lignin and its derivatives are complex mixtures: the purpose is to give a general idea of the structure of lignosulfonates. The groups R1 and R2 can be a wide variety of groups found in the structure of lignin. Sulfonation occurs on the side chains, not on the aromatic ring like in p-toluenesulfonic acid.

Generalized structure of lignosulfonates Ligninsulfonate Formation V2.svg
Generalized structure of lignosulfonates

Sulfonated Kraft lignin

Kraft lignin from black liquor, which is produced in much higher amounts, may be processed into sulfonated lignin. The lignin is first precipitated by acidifying the liquor with CO2 then washed (other methods for isolation exist). Reaction with sodium sulfite or sodium bisulfite and an aldehyde under a basic environment completes sulfonation. Here the sulfonic acid groups end up on the aromatic ring instead of the aliphatic sidechain. [3]

Uses

LS and SL have a wide variety of applications. They are used to stably disperse pesticides, dyes, carbon black, and other insoluble solids and liquids into water. As a binder it suppresses dust on unpaved roads. It is also a humectant and a in water treatment. [5] Chemically, it may be used as a tannin for tanning leather and as a feedstock for a variety of products.

Dispersant

The single largest use for lignosulfonates is as plasticizers in making concrete, [1] where they allow concrete to be made with less water (giving stronger concrete) while maintaining the ability of the concrete to flow. Lignosulfonates are also used during the production of cement, where they act as grinding aids in the cement mill and as a rawmix slurry deflocculant (that reduces the viscosity of the slurry).

Lignosulfonates are also used for the production of plasterboard to reduce the amount of water required to make the stucco flow and form the layer between two sheets of paper. The reduction in water content allows lower kiln temperatures to dry the plasterboard, saving energy.

The ability of lignosulfonates to reduce the viscosity of mineral slurries (deflocculation) is used to advantage in oil drilling mud, where it replaced tannic acids from quebracho (a tropical tree). Furthermore, lignosulphates are being researched for use in enhanced oil recovery (EOR) due to their ability to reduce interfacial tension in foams, allowing for improved sweep efficiency, and hence increased recovery factor.

Binder

Besides their use as dispersants lignosulfonates are also good binders. They are used as binders in well-paper, particle boards, linoleum flooring, coal briquettes, and roads.

They also form a constituent of the paste used to coat the lead-antimony-calcium or lead-antimony-selenium grids in a Lead-acid battery.

Aqueous lignosulfonate solutions are also widely used as a non-toxic dust suppression agent for unpaved road surfaces, where it is popularly, if erroneously, called "tree sap". Roads treated with lignosulfonates can be distinguished from those treated with calcium chloride by color: lignosulfonates give the road surface a dark grey color, while calcium chloride lend the road surface a distinctive tan or brown color. As lignosulfonates do not rely on water to provide their binding properties, they tend to be more useful in arid locations.

It is used as a soil stabilizer. [6]

Chemical feedstock

Oxidation of lignosulfonates from softwood trees produced vanillin (artificial vanilla flavor).

Dimethyl sulfide and dimethyl sulfoxide (an important organic solvent) are produced from lignosulfonates. The first step involves heating lignosulfonates with sulfides or elemental sulfur to produce dimethyl sulfide. The methyl groups come from methyl ethers present in the lignin. Oxidation of dimethyl sulfide with nitrogen dioxide produces dimethyl sulfoxide (DMSO). [1]

Other uses

The anti-oxidant effect of lignosulfonates is utilized in feeds, ensilage and flame retardants.

The UV absorbance of lignosulfonates is utilized in sun screens and bio-pesticides.

Lignosulfonate is used in agriculture as an analogue of humic substances. As a soil conditioner, it is mainly used to enhance the absorption and retention of fertilizers and other nutrients. [7] It is able to chelate minerals while remaining bio-degradable, an improvement compared to EDTA. [8] Further hydrolysis and oxidation produces a product even more similar to humus, marketed as "lignohumate". [9]

Related Research Articles

<span class="mw-page-title-main">Ether</span> Organic compounds made of alkyl/aryl groups bound to oxygen (R–O–R)

In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom bonded to two organyl groups. They have the general formula R−O−R′, where R and R′ represent the organyl groups. Ethers can again be classified into two varieties: if the organyl groups are the same on both sides of the oxygen atom, then it is a simple or symmetrical ether, whereas if they are different, the ethers are called mixed or unsymmetrical ethers. A typical example of the first group is the solvent and anaesthetic diethyl ether, commonly referred to simply as "ether". Ethers are common in organic chemistry and even more prevalent in biochemistry, as they are common linkages in carbohydrates and lignin.

Demethylation is the chemical process resulting in the removal of a methyl group (CH3) from a molecule. A common way of demethylation is the replacement of a methyl group by a hydrogen atom, resulting in a net loss of one carbon and two hydrogen atoms.

<span class="mw-page-title-main">Lignin</span> Structural phenolic polymer in plant cell walls

Lignin is a class of complex organic polymers that form key structural materials in the support tissues of most plants. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidity and do not rot easily. Chemically, lignins are polymers made by cross-linking phenolic precursors.

<span class="mw-page-title-main">Pulp (paper)</span> Fibrous material used notably in papermaking

Pulp is a fibrous lignocellulosic material prepared by chemically, semi-chemically or mechanically producing cellulosic fibers from wood, fiber crops, waste paper, or rags. Mixed with water and other chemicals or plant-based additives, pulp is the major raw material used in papermaking and the industrial production of other paper products.

<span class="mw-page-title-main">Methanethiol</span> Chemical compound

Methanethiol is an organosulfur compound with the chemical formula CH
3
SH
. It is a colorless gas with a distinctive putrid smell. It is a natural substance found in the blood, brain and feces of animals, as well as in plant tissues. It also occurs naturally in certain foods, such as some nuts and cheese. It is one of the chemical compounds responsible for bad breath and the smell of flatus. Methanethiol is the simplest thiol and is sometimes abbreviated as MeSH. It is very flammable.

<span class="mw-page-title-main">Anthraquinone</span> Yellow chemical compound: building block of many dyes

Anthraquinone, also called anthracenedione or dioxoanthracene, is an aromatic organic compound with formula C
14
H
8
O
2
. Isomers include various quinone derivatives. The term anthraquinone however refers to the isomer, 9,10-anthraquinone wherein the keto groups are located on the central ring. It is a building block of many dyes and is used in bleaching pulp for papermaking. It is a yellow, highly crystalline solid, poorly soluble in water but soluble in hot organic solvents. It is almost completely insoluble in ethanol near room temperature but 2.25 g will dissolve in 100 g of boiling ethanol. It is found in nature as the rare mineral hoelite.

<span class="mw-page-title-main">Plasticizer</span> Substance added to a material to make it softer and more flexible

A plasticizer is a substance that is added to a material to make it softer and more flexible, to increase its plasticity, to decrease its viscosity, and/or to decrease friction during its handling in manufacture.

<span class="mw-page-title-main">Kraft process</span> Process of converting wood into wood pulp

The kraft process (also known as kraft pulping or sulfate process) is a process for conversion of wood into wood pulp, which consists of almost pure cellulose fibres, the main component of paper. The kraft process involves treatment of wood chips with a hot mixture of water, sodium hydroxide (NaOH), and sodium sulfide (Na2S), known as white liquor, that breaks the bonds that link lignin, hemicellulose, and cellulose. The technology entails several steps, both mechanical and chemical. It is the dominant method for producing paper. In some situations, the process has been controversial because kraft plants can release odorous products and in some situations produce substantial liquid wastes.

<span class="mw-page-title-main">Sodium sulfite</span> Chemical compound

Sodium sulfite (sodium sulphite) is the inorganic compound with the chemical formula Na2SO3. A white, water-soluble solid, it is used commercially as an antioxidant and preservative. It is also suitable for the softening of lignin in the pulping and refining processes of wood and lignocellulosic materials. A heptahydrate is also known but it is less useful because of its greater susceptibility toward oxidation by air.

<span class="mw-page-title-main">Sulfonic acid</span> Organic compounds with the structure R−S(=O)2−OH

In organic chemistry, sulfonic acid refers to a member of the class of organosulfur compounds with the general formula R−S(=O)2−OH, where R is an organic alkyl or aryl group and the S(=O)2(OH) group a sulfonyl hydroxide. As a substituent, it is known as a sulfo group. A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound is the parent sulfonic acid, HS(=O)2(OH), a tautomer of sulfurous acid, S(=O)(OH)2. Salts or esters of sulfonic acids are called sulfonates.

<span class="mw-page-title-main">Pulp mill</span> Facility which pulps wood or plant fibre

A pulp mill is a manufacturing facility that converts wood chips or other plant fiber sources into a thick fiber board which can be shipped to a paper mill for further processing. Pulp can be manufactured using mechanical, semi-chemical, or fully chemical methods. The finished product may be either bleached or non-bleached, depending on the customer requirements.

<span class="mw-page-title-main">Aromatic sulfonation</span> Chemical reaction which replaces a hydrogen on an arene with sulfonic acid, –NH–SO3H

In organic chemistry, aromatic sulfonation is an organic reaction in which a hydrogen atom on an arene is replaced by a sulfonic acid functional group in an electrophilic aromatic substitution. Aryl sulfonic acids are used as detergents, dye, and drugs.

<span class="mw-page-title-main">Sodium dithionate</span> Chemical compound

Sodium dithionate Na2S2O6 is an important compound for inorganic chemistry. It is also known under names disodium dithionate, sodium hyposulfate, and sodium metabisulfate. The sulfur can be considered to be in its +5 oxidation state.

<span class="mw-page-title-main">Black liquor</span> Industrial by-product

In industrial chemistry, black liquor is the by-product from the kraft process when digesting pulpwood into paper pulp removing lignin, hemicelluloses and other extractives from the wood to free the cellulose fibers.

Bleaching of wood pulp is the chemical processing of wood pulp to lighten its color and whiten the pulp. The primary product of wood pulp is paper, for which whiteness is an important characteristic. These processes and chemistry are also applicable to the bleaching of non-wood pulps, such as those made from bamboo or kenaf.

The sulfite process produces wood pulp that is almost pure cellulose fibers by treating wood chips with solutions of sulfite and bisulfite ions. These chemicals cleave the bonds between the cellulose and lignin components of the lignocellulose. A variety of sulfite/bisulfite salts are used, including sodium (Na+), calcium (Ca2+), potassium (K+), magnesium (Mg2+), and ammonium (NH4+). The lignin is converted to lignosulfonates, which are soluble and can be separated from the cellulose fibers. For the production of cellulose, the sulfite process competes with the Kraft process which produces stronger fibers and is less environmentally costly.

<span class="mw-page-title-main">Calcium sulfite</span> Chemical compound

Calcium sulfite, or calcium sulphite, is a chemical compound, the calcium salt of sulfite with the formula CaSO3·x(H2O). Two crystalline forms are known, the hemihydrate and the tetrahydrate, respectively CaSO3·½(H2O) and CaSO3·4(H2O). All forms are white solids. It is most notable as the product of flue-gas desulfurization.

In industrial paper-making processes, organosolv is a pulping technique that uses an organic solvent to solubilise lignin and hemicellulose. It has been considered in the context of both pulp and paper manufacture and biorefining for subsequent conversion of cellulose to fuel ethanol. The process was invented by Theodor Kleinert in 1968 as an environmentally benign alternative to kraft pulping.

<span class="mw-page-title-main">Sodium bisulfite</span> Chemical compound

Sodium bisulfite (or sodium bisulphite, sodium hydrogen sulfite) is a chemical mixture with the approximate chemical formula NaHSO3. Sodium bisulfite in fact is not a real compound, but a mixture of salts that dissolve in water to give solutions composed of sodium and bisulfite ions. It appears in form of white or yellowish-white crystals with an odor of sulfur dioxide. Regardless of its ill-defined nature, sodium bisulfite is used in many different industries such as a food additive with E number E222 in the food industry, a reducing agent in the cosmetic industry, and a decomposer of residual hypochlorite used in the bleaching industry.

<span class="mw-page-title-main">Sodium 2-hydroxyethyl sulfonate</span> Chemical compound

Sodium 2-hydroxyethyl sulfonate is the sodium salt of 2-hydroxyethane sulfonic acid, it is used as a hydrophilic head group in washing-active surfactants, known as isethionates (acyloxyethanesulfonates) due to its strong polarity and resistance to multivalent ions. It is being studied as a high production volume chemical in the "High Production Volume (HPV) Chemical Challenge Program" of the US Environmental Protection Ministry EPA.

References

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  2. E. Sjöström (1993). Wood Chemistry: Fundamentals and Applications. Academic Press.
  3. 1 2 3 Aro, Thomas; Fatehi, Pedram (9 May 2017). "Production and Application of Lignosulfonates and Sulfonated Lignin". ChemSusChem. 10 (9): 1861–1877. Bibcode:2017ChSCh..10.1861A. doi: 10.1002/cssc.201700082 . PMID   28253428.
  4. "List of lignosulfonate CAS numbers" . Retrieved 2007-10-15.
  5. Barbara A. Tokay (2000). "Biomass Chemicals". Ullmann's Encyclopedia Of Industrial Chemistry. doi:10.1002/14356007.a04_099. ISBN   978-3527306732.
  6. Ta'negonbadi, Bahram; Noorzad, Reza (September 2017). "Stabilization of clayey soil using lignosulfonate". Transportation Geotechnics. 12: 45–55. Bibcode:2017TranG..12...45T. doi:10.1016/j.trgeo.2017.08.004.
  7. Wurzer, Gerhild K.; Hettegger, Hubert; Bischof, Robert H.; Fackler, Karin; Potthast, Antje; Rosenau, Thomas (23 February 2022). "Agricultural utilization of lignosulfonates". Holzforschung. 76 (2): 155–168. doi:10.1515/hf-2021-0114. S2CID   245021537.
  8. Cieschi, María T.; Benedicto, Ana; Hernández-Apaolaza, Lourdes; Lucena, Juan J. (28 November 2016). "EDTA Shuttle Effect vs. Lignosulfonate Direct Effect Providing Zn to Navy Bean Plants (Phaseolus vulgaris L 'Negro Polo') in a Calcareous Soil". Frontiers in Plant Science. 7: 1767. doi: 10.3389/fpls.2016.01767 . PMC   5147430 . PMID   28018367.
  9. Yakimenko, Olga; Stepanov, Andrey; Patsaeva, Svetlana; Khundzhua, Daria; Osipova, Olesya; Gladkov, Oleg (3 July 2021). "Formation of Humic-Like Substances during the Technological Process of Lignohumate® Synthesis as a Function of Time". Separations. 8 (7): 96. doi: 10.3390/separations8070096 .

See also