Author Topic: Purification of technical grade dichloromethane  (Read 61 times)

seeker

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Purification of technical grade dichloromethane
« on: March 28, 2012, 01:25:02 AM »
Technical grade dichloromethane is available in my neighborhood.

In addition to the usual technical grade impurities or stabilizers, the neighborhood DCM is packaged from the supplier in what appears to be an industrial grade HDPE (or similar) bottle instead of the expected metal can.  As lugh has pointed out in other contexts, there will also be impurities resulting from the bottle starting to dissolve and distillation at the minimum would be required before use.

The impurities may differ from those found in DCM isolated from paint strippers (good recent threads at SM on that subject).

Quote
IARC Monographs Volume 71--Dichloromethane:
Dichloromethane is available in several grades based on its intended end use: technical; aerosol; vapour degreasing; special; urethane; and decaffeination or Food Chemicals Codex/National Formula (food and pharmaceutical applications). Purity, when reported, ranges from 99 to 99.99%. Acidity (as hydrochloric acid) may be up to 5 mg/kg. The maximum concentration of water in these grades of dichloromethane is 100 mg/kg (Rossberg et al., 1986; Holbrook, 1993; Dow Chemical Co., 1995; Vulcan Chemicals, 1995, 1996a,b,c,d). Small amounts of stabilizers are often added to dichloromethane at the time of manufacture to protect against degradation by air and moisture. The following substances in the listed concentration ranges are the preferred additives (wt %): ethanol, 0.1–0.2; methanol, 0.1–0.2; cyclohexane, 0.01–0.03; and amylene (2-methyl-2-butene), 0.001–0.01. Other substances have also been described as being effective stabilizers, including phenols (phenol, hydroquinone, para-cresol, resorcinol, thymol, 1-naphthol), amines, nitroalkanes (nitromethane), aliphatic and cyclic ethers, epoxides, esters and nitriles (Rossberg et al., 1986; Holbrook, 1993).

Pure & App!. Chem., Vol. 59, No. 5, pp. 703—714, 1987.
The following specifications are representative of commercial grade (ref. 14) dichloromethane:
distillation range (101.3 kPa) 39.4 - 40.4°C
density 25°C 1.319 - 1.322 kg/dm3
acidity (as hydrogen chloride) 5 mg/kg
non-volatile matter 10 mg/kg
water 100 mg/kg

Although dichloromethane is considered to be relatively stable, small amounts of stabilizers may be used at the time of production and are found in the commercial product. Common stabilizers are phenolic compounds (phenol, hydroquinone, p-cresol for example), epoxides, amines, and a mixture of nitromethane and 1,4-dioxane (ref. 14).

The American Chemical Society standards for reagent grade dichloromethane include the following requirements (ref. 17): density, 1.321 to 1.315 kg/dm3; acidity (as hydrogen chloride), less than 0.001%; water, less than 0.02%. In addition, ACS spectroscopic grade dichloromethane standards require that the absorbance in a 1 cm cell not exceed 1.00 at 235 nm, 0.35 at 240 nm, 0.10 at 250 nm, 0.40 at 260 nm and 0.01 at 340 nm to 500 nm referred to water in a matched cell. Furthermore, the absorption curve should be smooth over the entire range of wavelengths.

PURIFICATION TECHNIQUES
The reported methods for the purification of dichloromethane are quite varied and reflect the different levels of purity needed for the particular experiment. For example, Lowry (ref. 18) fractionally distilled commercial dichloromethane many times until the conductivity of the middle fraction was constant, while Gray (ref. 19) reports that dichloromethane can be purified by vacuum distillation onto activated 4A molecular sieves and distilled again when needed.

The most common method for purification of dichloromethane is to reflux the solvent under an inert gas over a drying agent, such as phosphorous pentoxide or calcium hydride, followed by distillation as needed (20—23). Molecular sieves (4A) are frequently used for storing and drying the dichloromethane rather than phosphorous pentoxide or calcium hydride. A variation of the same technique described above is to distill the solvent from lithium aluminum hydride under argon (ref. 24) or to doubly distill dichloromethane from phosphorous pentoxide under argon followed by a final distillation from potassium carbonate (ref. 25).

A more rigorous purification method involves pre-washing dichloromethane, followed by distillation. For example, Maryott (ref. 26) washed commercial dichloromethane with concentrated sulfuric acid, then with aqueous sodium hydroxide, followed by water. The dichloromethane was then dried by leaving overnight over sodium hydroxide and calcium chloride. Finally, the product was fractionally distilled. Perrin (ref. 27) reports a method for the purification of dichloromethane that is similar to MaryotUs. Perrin's method is to shake the dichloromethane with concentrated sulfuric acid until the acid layer remains colorless, wash with water, 5% aqueous sodium carbonate and then water again. The dichloromethane is pre-dryed with calcium chloride, distilled from calcium hydride or phosphorous pentoxide, and stored over activated 4A molecular sieves. This method is used quite frequently (ref. 28, 29).

RECOMMENDED PROCEDURE FOR DICHLOROMETHANE
The recommended procedure is based on Perrin's technique, but with some modification. Shake reagent grade dichloromethane with concentrated sulfuric acid until the acid layer remains colorless. Wash with water, saturated aqueous sodium carbonate, and then with water again. Pre-dry with calcium chloride. Ref lux for two hours over phosphorous pentoxide and distill onto fresh phosphorous pentoxide under inert atmosphere, discarding the first 10% and the last 20% of the solvent. The dichloromethane can then be stored over phosphorous pentoxide and distilled as needed.

Vogel 3rd ed.:
Methylene chloride. The commercial substance is purified by washing with 5 per cent. sodium carbonate solution, followed by water,
dried over anhydrous calcium chloride, and then fractionated. The
fraction, b.p. 40-41°, is collected.

Vogel 5th ed.:
Dichloromethane (methylene chloride)
The commercial grade is purified by washing with portions of concentrated sulphuric acid until the acid layer remains colourless, and then with water, sodium carbonate solution and water again.  It is initially dried over calcium chloride and then distilled from calcium hydride before use.  The fraction b.p. 40-41° C is collected.  Dichloromethane should be stored in a brown bottle away from light over Type 3A molecular sieve.

Purification of Laboratory Chemicals:
Dichloromethane M 84.9, b 40.0°, d 1.325, n 1.42456,n251.4201.
Shaken with portions of conc H2SO4 until the acid layer remained colourless, then washed with water, aqueous 5% Na2C03, NaHCO3 or NaOH, then water again. Pre-dried with CaC12, and distd from CaSO4, CaH2 or P2O5. Stored away from bright light in a brown bottle with Linde type 4A molecular sieves, in an atmosphere of dry N2. Other purification steps include washing with aq Na2S203, passage through a column of silica gel, and removal of carbonyl-containing impurities as described under Chloroform. It has also been
purified by treatment with basic alumina, distd, and stored over molecular sieves under nitrogen [Puchot et al. J Am Chem SOC 108 2353 19861.

Dichloromethane from Japanese sources contained MeOH as stabiliser which is not removed by distn. It can, however, be removed by standing over activated 3A Molecular Sieves (note that 4A Sieves cause the development of pressure in bottles), passed through activated A1203 and distd [Gao et al. J Am Chem Soc 109 5771 19871. It has been fractionated through a platinum spinning band column, degassed, and distd onto degassed molecular sieves, Linde 4A, heated under high vacuum at over 450 until the pressure readings reached the low values of 10(-6)mm - -1-2h [Mohammad and Kosower J Am Chem SOC 93 2713 19711.  Rapid purification: Reflux over CaH2 (5% w/v) and distil. Store over 4A molecular sieves.

The only UTFSE reference I found to use of technical grade DCM was by Dr. Drool in the Wacker reaction, nothing on purification.

There are several considerations here.

A stabilizer with a double bond such as amylene, if present, would react under many experimental conditions, garbage in, garbage out.  Since it has a reported boiling point of 35-38C, a wash with H2SO4 drain cleaner (what’s available in the neighborhood) might be preferable to distillation or fractional distillation as a means of removal.  Of course, drain cleaner might conceivably introduce as many impurities as it removes,

Alcohols would also react under some conditions, removal via an aqueous calcium chloride wash and anhydrous CaCl2 drying procedure would again probably be preferable to distillation due to azeotropes (maybe the wash could be skipped if drying with CaCl2).

Phenols, quinones, epoxides, amines, esters, nitromethane, etc. are also not desired.

So hypothetical purification procedures, depending on envisioned use, would be: 1) a wash with H2SO4 followed by water/base/water/aqueous calcium chloride washes, CaCl2 drying and fractional distillation, 2) a wash with H2SO4 followed by water/base/water washes, CaCl2 drying and fractional distillation, 3) a Vogel 3rd wash with carbonate, dry and fractionally distill, or 4) simply fractionally distill.

Any thoughts or advice by those with more experience or knowledge?

lugh

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Re: Purification of technical grade dichloromethane
« Reply #1 on: March 28, 2012, 01:58:44 AM »
Which choice of purification methods would be best would depend on what the prospective use of this dichloromethane actually was  ;) If it's being used a solvent in a peracid epoxidation then there's probably no need for a rigorous purification since polyethylene is much more inert that polyethylene terephathalate  :P  The most common contaminant according to an old textbook is methyl chloride  :-X  That shouldn't interfere with a peracid epoxidation  8)
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fresh1

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Re: Purification of technical grade dichloromethane
« Reply #2 on: March 28, 2012, 05:36:53 AM »
Quote
If it's being used a solvent in a peracid epoxidation then there's probably no need for a rigorous purification since polyethylene is much more inert that polyethylene terephathalate  :P  The most common contaminant according to an old textbook is methyl chloride  :-X  That shouldn't interfere with a peracid epoxidation  8)

 thats what we want to hear lughmon, your experience makes you king ;)
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