Lignosulfonates (LS) are water-soluble anionic

polyelectrolyte Polyelectrolytes are polymers whose repeating units bear an electrolyte group. Polycations and polyanions are polyelectrolytes. These groups dissociate in aqueous solutions (water), making the polymers charged. Polyelectrolyte properties are t ...

polymer A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...

s: they are byproducts from the production of

wood pulp Pulp is a fibrous Lignocellulosic biomass, lignocellulosic material prepared by chemically, semi-chemically, or mechanically isolating the cellulose fiber, cellulosic fibers of wood, fiber crops, Paper recycling, waste paper, or cotton paper, rag ...

using sulfite pulping. Most delignification in sulfite pulping involves acidic cleavage of

ether In organic chemistry, ethers are a class of compounds that contain an ether group, a single oxygen atom bonded to two separate carbon atoms, each part of an organyl group (e.g., alkyl or aryl). They have the general formula , where R and R� ...

bonds, which connect many of the constituents of

lignin 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 rigidit ...

. Sulfonated lignin (SL) refers to other forms of lignin by-product, such as those derived from the much more popular

Kraft process 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 chip ...

, 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. LS and SL both appear as free-flowing powders; the former is light brown while the latter is dark brown. Lignosulfonates have very broad ranges of

molecular mass The molecular mass () is the mass of a given molecule, often expressed in units of daltons (Da). Different molecules of the same compound may have different molecular masses because they contain different isotopes of an element. The derived quan ...

(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. SL and LS are non-toxic, non-corrosive, and

biodegradable Biodegradation is the breakdown of organic matter by microorganisms, such as bacteria and fungi. It is generally assumed to be a natural process, which differentiates it from composting. Composting is a human-driven process in which biodegrada ...

. A range of further modifications may be applied to LS and SL, including oxidation, hydroxymethylation, sulfomethylation, and a combination thereof.

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. A list of CAS numbers for the various metal salts of lignosulfonate is available. The

electrophilic In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carr ...

carbocation Carbocation is a general term for ions with a positively charged carbon atom. In the present-day definition given by the IUPAC, a carbocation is any even-electron cation with significant partial positive charge on a carbon atom. They are further ...

s 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. Ligninsulfonate Formation V2

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 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 In organic chemistry, hydrocarbons ( compounds composed solely of carbon and hydrogen) are divided into two classes: aromatic compounds and aliphatic compounds (; G. ''aleiphar'', fat, oil). Aliphatic compounds can be saturated (in which all ...

sidechain.

Uses

LS and SL have a wide variety of applications. They are used to stably disperse

pesticides Pesticides are substances that are used to pest control, control pest (organism), pests. They include herbicides, insecticides, nematicides, fungicides, and many others (see table). The most common of these are herbicides, which account for a ...

dyes Juan de Guillebon, better known by his stage name DyE, is a French musician. He is known for the music video of the single "Fantasy (DyE song), Fantasy" from his first album ''Taki 183 (album), Taki 183''. This video became popular, attracting ...

carbon black Carbon black (with subtypes acetylene black, channel black, furnace black, lamp black and thermal black) is a material produced by the incomplete combustion of coal tar, vegetable matter, or petroleum products, including fuel oil, fluid cataly ...

, and other insoluble solids and liquids into water. As a

binder Binder may refer to: Businesses * Binder FBM, a former German jewelry manufactory * Binder Dijker Otte & Co., the expansion of "BDO" in BDO International Computing * Binder Project, package and share interactive, reproducible environments * Fil ...

it suppresses dust on unpaved roads. It is also a

humectant A humectant is a hygroscopic (water-absorbing) substance used to keep things moist. They are used in many products, including food, cosmetics, medicines and pesticides. When used as a food additive, a humectant has the effect of keeping moistu ...

and a in

water treatment Water treatment is any process that improves the quality of water to make it appropriate for a specific end-use. The end use may be drinking, industrial water supply, irrigation, river flow maintenance, water recreation or many other uses, ...

. Chemically, it may be used as a

tannin Tannins (or tannoids) are a class of astringent, polyphenolic biomolecules that bind to and Precipitation (chemistry), precipitate proteins and various other organic compounds including amino acids and alkaloids. The term ''tannin'' is widel ...

for tanning

leather Leather is a strong, flexible and durable material obtained from the tanning (leather), tanning, or chemical treatment, of animal skins and hides to prevent decay. The most common leathers come from cattle, sheep, goats, equine animals, buffal ...

and as a feedstock for a variety of products.

Dispersant

The single largest use for lignosulfonates is as

plasticizers A plasticizer (British English, UK: plasticiser) is a substance that is added to a material to make it softer and more flexible, to increase its plasticity (physics), plasticity, to decrease its viscosity, and/or to decrease friction during its ...

in making

concrete Concrete is a composite material composed of aggregate bound together with a fluid cement that cures to a solid over time. It is the second-most-used substance (after water), the most–widely used building material, and the most-manufactur ...

, 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 A cement is a binder, a chemical substance used for construction that sets, hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel ( aggregate) together. Cement mi ...

, where they act as grinding aids in the cement mill and as a rawmix slurry

deflocculant In colloidal chemistry, flocculation is a process by which colloidal particles come out of suspension to sediment in the form of floc or flake, either spontaneously or due to the addition of a clarifying agent. The action differs from precipit ...

(that reduces the

viscosity Viscosity is a measure of a fluid's rate-dependent drag (physics), resistance to a change in shape or to movement of its neighboring portions relative to one another. For liquids, it corresponds to the informal concept of ''thickness''; for e ...

of the slurry). Lignosulfonates are also used for the production of

plasterboard Drywall (also called plasterboard, dry lining, wallboard, sheet rock, gib board, gypsum board, buster board, turtles board, slap board, custard board, gypsum panel and gyprock) is a panel made of calcium sulfate dihydrate (gypsum), with or witho ...

to reduce the amount of water required to make the

stucco Stucco or render is a construction material made of aggregates, a binder, and water. Stucco is applied wet and hardens to a very dense solid. It is used as a decorative coating for walls and ceilings, exterior walls, and as a sculptural and ...

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 An oil well is a drillhole boring (earth), boring in Earth that is designed to bring petroleum oil hydrocarbons to the surface. Usually some natural gas is released as associated petroleum gas along with the oil. A well that is designed to produ ...

mud Mud (, or Middle Dutch) is loam, silt or clay mixed with water. Mud is usually formed after rainfall or near water sources. Ancient mud deposits hardened over geological time to form sedimentary rock such as shale or mudstone (generally cal ...

, where it replaced

tannic acid Tannic acid is a specific form of tannin, a type of polyphenol. Its weak acidity (Acid dissociation constant, pKa around 6) is due to the numerous phenol groups in the structure. The chemical formula for commercial tannic acid is often given as ...

s from quebracho (a tropical tree). Furthermore, lignosulphates are being researched for use in

enhanced oil recovery Enhanced oil recovery (abbreviated EOR), also called tertiary recovery, is the extraction of crude oil from an oil field that cannot be extracted after primary and secondary recovery methods have been completely exhausted. Whereas primary and se ...

(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 Calcium chloride is an inorganic compound, a Salt (chemistry), salt with the chemical formula . It is a white crystalline solid at room temperature, and it is highly soluble in water. It can be created by neutralising hydrochloric acid with cal ...

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.

Chemical feedstock

Oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...

of lignosulfonates from

softwood Scots pine, a typical and well-known softwood Softwood is wood from gymnosperm trees such as conifers. The term is opposed to hardwood, which is the wood from angiosperm trees. The main differences between hardwoods and softwoods is that the sof ...

trees produced

vanillin Vanillin is an organic compound with the molecular formula . It is a phenolic aldehyde. Its functional groups include aldehyde, hydroxyl, and ether. It is the primary component of the ethanolic extract of the vanilla bean. Synthetic vanillin ...

(artificial vanilla flavor).

Dimethyl sulfide Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula . It is the simplest thioether and has a characteristic disagreeable odor. It is a flammable liquid that boils at . It is a component of the smell produc ...

and

dimethyl sulfoxide Dimethyl sulfoxide (DMSO) is an organosulfur compound with the formula . This colorless liquid is the sulfoxide most widely used commercially. It is an important polar aprotic solvent that dissolves both polar and nonpolar compounds and is ...

(an important organic

solvent A solvent (from the Latin language, Latin ''wikt:solvo#Latin, solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a Solution (chemistry), solution. A solvent is usually a liquid but can also be a solid, a gas ...

) are produced from lignosulfonates. The first step involves heating lignosulfonates with

sulfides Sulfide (also sulphide in British English) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to large families of ...

or elemental

sulfur Sulfur ( American spelling and the preferred IUPAC name) or sulphur ( Commonwealth spelling) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms ...

to produce dimethyl sulfide. The

methyl In organic chemistry, a methyl group is an alkyl derived from methane, containing one carbon atom bonded to three hydrogen atoms, having chemical formula (whereas normal methane has the formula ). In formulas, the group is often abbreviated as ...

groups come from methyl ethers present in the lignin. Oxidation of dimethyl sulfide with

nitrogen dioxide Nitrogen dioxide is a chemical compound with the formula . One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, is an intermediate in the s ...

produces dimethyl sulfoxide (DMSO).

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 A soil conditioner is a product which is added to soil to improve the soil’s physical qualities, usually its fertility (ability to provide nutrition for plants) and sometimes its mechanics. In general usage, the term "soil conditioner" is often ...

, it is mainly used to enhance the absorption and retention of fertilizers and other nutrients. It is able to

chelate Chelation () is a type of bonding of ions and their molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These l ...

minerals while remaining bio-degradable, an improvement compared to

EDTA Ethylenediaminetetraacetic acid (EDTA), also called EDTA acid, is an aminopolycarboxylic acid with the formula . This white, slightly water-soluble solid is widely used to bind to iron (Fe2+/Fe3+) and calcium ions (Ca2+), forming water-solubl ...

. Further hydrolysis and oxidation produces a product even more similar to

humus In classical soil science, humus is the dark organic matter in soil that is formed by the decomposition of plant and animal matter. It is a kind of soil organic matter. It is rich in nutrients and retains moisture in the soil. Humus is the Lati ...

, marketed as "lignohumate".