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 ...

polymer A polymer (; Greek '' poly-'', "many" + '' -mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...

s: they are byproducts from the production of

wood pulp Pulp is a lignocellulosic fibrous material prepared by chemically or mechanically separating cellulose fibers from wood, fiber crops, waste paper, or rags. Mixed with water and other chemical or plant-based additives, pulp is the major raw ...

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—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again ...

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 rigidity a ...

. 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 (''m'') is the mass of a given molecule: it is measured in daltons (Da or u). Different molecules of the same compound may have different molecular masses because they contain different isotopes of an element. The related quant ...

(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. AA 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 A carbocation is an ion with a positively charged carbon atom. Among the simplest examples are the methenium , methanium and vinyl cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encount ...

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 In organic chemistry, propyl is a three-carbon alkyl substituent with chemical formula for the linear form. This substituent form is obtained by removing one hydrogen atom attached to the terminal carbon of propane. A propyl substituent is often ...

(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 ''p''-Toluenesulfonic acid (PTSA or ''p''TsOH) or tosylic acid (TsOH) is an organic compound with the formula CH3 C6H4 SO3H. It is a white extremely hygroscopic solid that is soluble in water, alcohols, and other polar organic solvents. The CH3C ...

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, like hexane ...

sidechain.

Uses

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

pesticides Pesticides are substances that are meant to control pests. This includes herbicide, insecticide, nematicide, molluscicide, piscicide, avicide, rodenticide, bactericide, insect repellent, animal repellent, microbicide, fungicide, and la ...

dyes A dye is a colored substance that chemically bonds to the substrate to which it is being applied. This distinguishes dyes from pigments which do not chemically bind to the material they color. Dye is generally applied in an aqueous solution an ...

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

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

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, inc ...

. Chemically, it may be used as a

tannin Tannins (or tannoids) are a class of astringent, polyphenolic biomolecules that bind to and precipitate proteins and various other organic compounds including amino acids and alkaloids. The term ''tannin'' (from Anglo-Norman ''tanner'' ...

for

tanning Tanning may refer to: *Tanning (leather), treating animal skins to produce leather *Sun tanning, using the sun to darken pale skin **Indoor tanning, the use of artificial light in place of the sun **Sunless tanning, application of a stain or dye t ...

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

and as a feedstock for a variety of products.

Dispersant

The single largest use for lignosulfonates is as

plasticizers A plasticizer ( UK: plasticiser) 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. Plastic ...

in making

concrete Concrete is a composite material composed of fine and coarse aggregate bonded together with a fluid cement (cement paste) that hardens (cures) over time. Concrete is the second-most-used substance in the world after water, and is the most wid ...

, 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 mixe ...

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

rawmix Portland cement is the most common type of cement in general use around the world as a basic ingredient of concrete, mortar, stucco, and non-specialty grout. It was developed from other types of hydraulic lime in England in the early 19th cen ...

slurry

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

(that reduces the

viscosity The viscosity of a fluid is a measure of its resistance to deformation at a given rate. For liquids, it corresponds to the informal concept of "thickness": for example, syrup has a higher viscosity than water. Viscosity quantifies the int ...

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

plasterboard Drywall (also called plasterboard, dry lining, wallboard, sheet rock, gypsum board, buster board, custard board, and gypsum panel) is a panel made of calcium sulfate dihydrate (gypsum), with or without additives, typically extruded between thick ...

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 a ...

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 is used to advantage in

oil drilling An oil well is a drillhole 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 produce only gas may ...

mud, where it replaced

tannic acid Tannic acid is a specific form of tannin, a type of polyphenol. Its weak acidity ( pKa around 6) is due to the numerous phenol groups in the structure. The chemical formula for commercial tannic acid is often given as C76H52O46, which corresp ...

s from quebracho (a tropical tree). Also one of the very wide uses of lignosulfonates is deflocculation of clays used in drilling fluids in the oil and gas industry. 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 otherwise. EOR can extract 30% to 60% or more of a reservoir's oil, compared to 20% to 40% using ...

(EOR) due to their ability to reduce IFT 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 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 calcium hydroxide. Ca ...

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

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 s ...

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 extract of the vanilla bean. Synthetic vanillin is now u ...

(artificial vanilla flavor).

Dimethyl sulfide Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. Dimethyl sulfide is a flammable liquid that boils at and has a characteristic disagreeable odor. It is a component of the smell produced from co ...

and

dimethyl sulfoxide Dimethyl sulfoxide (DMSO) is an organosulfur compound with the formula ( CH3)2. This colorless liquid is the sulfoxide most widely used commercially. It is an important polar aprotic solvent that dissolves both polar and nonpolar compounds a ...

(an important organic

solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...

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

sulfides Sulfide (British English also sulphide) 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 chemical compounds la ...

or elemental

sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formul ...

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 . In formulas, the group is often abbreviated as Me. This hydrocarbon group occurs in ...

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 . It is one of several nitrogen oxides. is an intermediate in the industrial synthesis of nitric acid, millions of tons of which are produced each year for use primarily in the productio ...

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 are 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 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 ligands are ...

minerals while remaining bio-degradable, an improvement compared to

EDTA Ethylenediaminetetraacetic acid (EDTA) is an aminopolycarboxylic acid with the formula H2N(CH2CO2H)2sub>2. This white, water-soluble solid is widely used to bind to iron (Fe2+/Fe3+) and calcium ions (Ca2+), forming water-soluble complexes ev ...

. 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".