544-17-2

Basic information

• Product Name: Calcium formate
• Synonyms: calciumdiformate;calciumformate(ca(hco2)2);calcoform;formatedecalcium;mravencanvapenaty;mravencanvapenaty(czech);CALCIUM FORMATE;FORMIC ACID CALCIUM SALT
• CAS NO: 544-17-2
• Molecular Formula: 2CHO₂*Ca
• Molecular Weight: 130.11
• EINECS: 208-863-7
• Product Categories: INORGANIC & ORGANIC CHEMICALS;Preservatives. Have a diuretic effect;Pharmaceutical intermediates;Fine Chemical&Feed Additives
• Mol File: 544-17-2.mol
• Article Data: 13

Chemical Properties

• Melting Point: 300 °C
• Boiling Point: 100.6 °C at 760 mmHg
• Flash Point: 29.9 °C
• Appearance: /orthorhombic crystals
• Density: 2,02 g/cm3
• Vapor Pressure: 3.41Pa at 25℃
• Storage Temp.: Inert atmosphere,Room Temperature
• Solubility: H2O: 1 M at 20 °C, clear, colorless
• PKA: 3.8[at 20 ℃]
• Water Solubility: SOLUBLE
• Merck: 13,1670
• BRN: 3624099
• CAS DataBase Reference: Calcium formate(CAS DataBase Reference)
• NIST Chemistry Reference: Calcium formate(544-17-2)
• EPA Substance Registry System: Calcium formate(544-17-2)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38-41
• Safety Statements: 26-37/39-39-24/2526
• WGK Germany: 1
• RTECS: LQ5600000
• TSCA: Yes
• Hazardous Substances Data: 544-17-2(Hazardous Substances Data)

Usage

Description

Calcium formate, also known as calcium hydrogen formate, is a white to almost white fine crystalline powder. It is the calcium salt of formic acid, with the chemical formula Ca(HCOO)2. Calcium formate is used in various industries due to its unique properties, such as being an organic salt, a preservative, and an acidifying agent.

Uses

Used in Construction Materials:
Calcium formate is used as a hydrophobic additive for construction materials, enhancing their water resistance and durability.
Used in Energy Production:
Formic acid, derived from calcium formate, is used as a potential energy source in the preparation of fuel cells, making it a valuable component in the renewable energy sector.
Used in Chemical Synthesis:
Calcium formate is utilized in the chemical synthesis of various anti-inflammatory and anti-microbial agents, contributing to the development of pharmaceuticals and healthcare products.
Used in Food Preservation and Silage:
Calcium formate serves as a preservative for food and silage, extending the shelf life and maintaining the quality of these products.
Used in Mining and Drilling:
It acts as a binder for fine-ore briquets, improving the efficiency of mining operations. Additionally, it is used in drilling fluids and lubricants, enhancing the performance of these materials.
Used in Animal Feed Industry:
Calcium formate is an organic salt suitable for use in pig and poultry diets, acting as a feedstock preservative and promoting good gut-health. It has an acidifying effect on the gastro-intestinal tract, which helps in the efficient digestion of feedstock and limits the proliferation of pathogenic bacteria.
Used in Leather Industry:
Calcium formate is extensively used in the leather industry as a masking agent in the chrome-tanning process. It promotes faster and more efficient penetration of the chrome in the leather and can also replace formic acid in the pickling operation.
Used in Cement Production:
Calcium formate is used as an accelerator for pozzolanic cement pastes, shortening the initial and final setting times, and increasing the compressive strength, combined water content, and gel/space ratio at all ages of hydration. It also decreases the total porosity, improving the overall quality of the cement.

Reactions

Calcium formate can be used to prepare solutions of other water-soluble formate salts. For example, the addition of nickel (II) sulfate to a solution of calcium formate results in the precipitation of insoluble calcium sulfate, leaving nickel (II) formate in solution: Ca(OOCH)2 + NiSO1 → CaSO4 + Ni(OOCH)2 In a similar reaction, sulfuric acid reacts with calcium formate to provide low-cost solutions of formic acid: Ca(OOCH)2 + H2 SO4 → CaSO4 + 2HCOOH When heated, calcium formate decomposes to calcium carbonate and formaldehyde: Ca(OOCH)2 → CaCO3 + HCHO Calcium formate can be used as a low-cost reducing agent in the conversion of carboxylic acids to aldehydes. This process is an effective substitute for the troublesome Rosenmund reduction. (RCOO)2Ca + (HCOO)2CA → 2RCH + 2CaCO3

Flammability and Explosibility

Notclassified

Safety Profile

Poison by intravenous route. Moderately toxic by ingestion. An eye irritant. When heated to decomposition it emits acrid smoke and fumes. See also CALCIUM COMPOUNDS.

Purification Methods

Recrystallise it from water (5mL/g) by partial evaporation in a desiccator. [Beilstein 2 IV 16.]

Toxicity evaluation

Calcium formate has a low order of toxicity. In rats, the acute oral LD50 is 2650mg/kg; by intravenous injection, the LD50 is 154mg/kg. In a study with rats, calcium formate added to the drinking water at 0.2% for 3 years or 0.4% for 2 years didn't affect growth, fertility or function in up to 5 generations. Calcium formate would be expected to be irritating to the eyes and skin. In case of eye contact, immediately flush the eyes with water for 15 minutes. Avoid prolonged or repeated exposure of the skin.

References

Heikal, Mohamed. "Effect of calcium formate as an accelerator on the physicochemical and mechanical properties of pozzolanic cement pastes." Cement & Concrete Research 34.6(2004):1051-1056. Bosi, P, et al. "The influence of fat protection of calcium formate on growth and intestinal defense in Escherichia coli K88-challenged weanling pigs." Animal Feed Science & Technology 139.3–4(2007):170-185. Bolze, Rudolf, et al. "Agent for increasing the performance of pigs and poultry." EP, EP0260391. 1988.

InChI:InChI=1/CH2O2.Ca/c2-1-3;/h1H,(H,2,3);/q;+2/p-1

Synthetic route

carbon monoxide (201230-82-2) + water (7732-18-5) + calcium oxide → calcium diformate (544-17-2)

Conditions	Yield
In water heating suspension of 240 g pure CaCO3 in 1 l H2O with CO for few hours in Fe shaker autoclave at 20-45 at and 160°C, until there is no redn. of pressure; after cooling, diln. with hot H2O, filtration; pptn. of Ca(OH)2 with CO2; filtration;; vaporization of filtrate; pptn.;;	92%
In water heating suspension of 240 g pure CaCO3 in 1 l H2O with CO for few hours in Fe shaker autoclave at 20-45 at and 160°C, until there is no redn. of pressure; after cooling, diln. with hot H2O, filtration; pptn. of Ca(OH)2 with CO2; filtration;; vaporization of filtrate; pptn.;;	92%

sodium formate *3H2O (51437-68-4, 100462-49-5, 104959-61-7) → calcium diformate (544-17-2)

carbon monoxide (201230-82-2) → calcium diformate (544-17-2)

Conditions	Yield
With calcium hydroxide at 180℃; under 36775.4 Torr; Product distribution; temperatures from 100 to 200 deg C, pressure from 30 to 60 kg/cm2, effect of Ca(OH)2 concentration, optimal conditions for maximum yield achievement;
With methylamine; calcium hydroxide at 165 - 170℃; Temperature; Reagent/catalyst;

formic acid (64-18-6) + calcium carbonate → calcium diformate (544-17-2)

Conditions	Yield
In water
In not given
In formic acid addn. of excessive, fresh pptd. CaCO3 to diluted formic acid; first at ambient temp., then heating; filtration;; vaporization of filtrate; solving of residue on water bath with water; storage on a warm place; crystn. of H2O free calcium formate;;

carbon dioxide (124-38-9) → calcium diformate (544-17-2)

Conditions	Yield
With water; hydrogen; palladium; calcium carbonate
With borax; water; hydrogen; palladium
With borax; water; hydrogen; palladium
With water; hydrogen; palladium; calcium carbonate

Upstream product

• 51437-68-4 sodium formate *3H₂O 
• 201230-82-2 carbon monoxide 
• 64-18-6 formic acid 
• 124-38-9 carbon dioxide 
• 156-62-7 calcium cyanamide 
• 7732-18-5 water 
• 14336-71-1 calcium chloride 
• 1333-74-0 hydrogen 
• 71-47-6 formate 
• 50-00-0 formaldehyd 
• 75-07-0 acetaldehyde 
• 3812-32-6 carbonate^(2-) 
• 7789-78-8 calcium hydride 
• 590-29-4 potassium formate 

Downstream Products

• 120-72-9 indole 
• 98-86-2 acetophenone 
• 66-77-3 1-naphthaldehyde 
• 69-89-6 xanthin 
• 111-87-5 octanol 
• 584-08-7 potassium carbonate 
• 62-54-4 calcium acetate 
• 13494-80-9 hydrogen telluride 
• 557-41-5 zinc(II) formate 
• 141-53-7 sodium formate 
• 7360-53-4 aluminium triformate 
• 540-69-2 ammonium formate 
• 590-29-4 potassium formate 
• 127099-85-8 dicyandiamide 

Relevant articles and documents

Hydrogenation of aqueous mixtures of calcium carbonate and carbon dioxide using a water-soluble rhodium(I)-tertiary phosphine complex catalyst

Aqueous suspensions of calcium carbonate were hydrogenated to yield calcium formate under a gas phase containing both H2 and CO2. A rhodium(I)-complex of monosulfonated triphenylphosphine (mtppms), [RhCl(mtppms)3] was used as catalyst. Reaction temperatures were in the range of 20-70°C, total pressure 10-100 bar with an optimum p(CO 2):p(H2) ratio of 1:4. Due to the mobile bicarbonate-formate equilibrium, the highest available formate concentration is decreased with increasing temperature but increased with increasing pressure. Interestingly, at 50°C and 100 bar total pressure the yield of formate was 143% (based on CaCO3) which implies the formation of free formic acid in the reaction of CO2 from the gas phase. The dependence of the hydrogenation rate on the catalyst and ligand concentrations, as well as that of the decomposition of formate as a function of temperature were also studied. A mild method has been developed for the hydrogenation of calcium carbonate to calcium formate in aqueous suspensions under CO2 + H2 pressure catalyzed by [RhCl(mtppms)3] (mtppms = monosulfonated triphenylphosphine) at 20-70°C and 10-100 bar total pressure. In certain cases the yield of formate exceeded 100% (based on CaCO3) which implies the concomitant hydrogenation of carbon dioxide, too.

Eco-friendly upconversion of limestone into value-added calcium formate

Although CaCO3 is a naturally available, inexpensive, abundant and extensively used chemical in various industries, to date, most of its conversions liberate CO2 into the atmosphere, which accounts for about 5-6% of global anthropogenic CO2 emission. Herein, the first synthesis of calcium formate (CF) by hydrogenation of an aqueous mixture of CaCO3 and CO2 using a heterogeneous catalyst in an unconventional CO2 reducing manner is reported. The phosphine-based heterogenized Ru catalyst efficiently converts CaCO3 into CF with good selectivity (>99%) and is readily separated from the reaction product, resulting in promising recycling ability. Thus, this work provides a promising strategy for the design of green and sustainable conversion of carbonate minerals in industry.

A a method of preparing calcium

The invention discloses a preparation method of calcium formate and belongs to the technical field of chemical synthesis. The preparation method of the calcium formate comprises the following steps: carrying out dust removal on semi-water gas, desulphurizing, compressing, carbonizing and recompressing to 3-5MPa to obtain feed gas, reacting with a calcium hydroxide turbid liquid in the presence of ammonia or amine to generate a calcium formate aqueous solution containing ammonium formate or amine formate, adding right amount of lime milk and carrying out a replacement reaction in a calcium formate aqueous solution concentrating process, so that calcium formate precipitate is obtained. The preparation method of the calcium formate has the advantages that a reaction accelerator volatile alkali is used in a process that the feed gas reacts with the calcium hydroxide turbid liquid, generation of formate ions in reaction between carbon monoxide and hydroxyl ions is sped up, and concentration of a formate solution generated by the reaction between the carbon monoxide and hydroxyl ions is greatly increased, so that energy consumption in a concentration process is reduced, and coproduction of calcium formate and sodium formate can be realized on the basis of the original synthetic ammonia production system.