Recovery formic acid

Although acetic acid and water are not beheved to form an azeotrope, acetic acid is hard to separate from aqueous mixtures. Because a number of common hydrocarbons such as heptane or isooctane form azeotropes with formic acid, one of these hydrocarbons can be added to the reactor oxidate permitting separation of formic acid. Water is decanted in a separator from the condensate. Much greater quantities of formic acid are produced from naphtha than from butane, hence formic acid recovery is more extensive in such plants. Through judicious recycling of the less desirable oxygenates, nearly all major impurities can be oxidized to acetic acid. Final acetic acid purification follows much the same treatments as are used in acetaldehyde oxidation. Acid quahty equivalent to the best analytical grade can be produced in tank car quantities without difficulties. 

This latter situation affords a good method for separating uranium from plutonium. Hydroxylammonium formate (HAF) and hydrazium formate (NHF) were added to the formic acid to reduce Pu(IV) to Pu(III) to aid in plutonium recovery, although formic acid alone will strip tetravalent actinides, e.g., Th(IV) from 0D[IB]CMP0, once excess HNO3 present in the organic phase is removed. Thus, formic acid with HAF and NHF affords an excellent method for stripping all the actinides from these very powerful CMP extractants. Under the above conditions Am(III) and Cm(III) present in... 

Dissolution/reprecipitation processes were evaluated for the recycling of poly-epsilon-caprolactam (PA6) and polyhexamethyleneadipamide (PA66). The process involved solution of the polyamide in an appropriate solvent, precipitation by the addition of a non-solvent, and recovery of the polymer by washing and drying. Dimethylsulphoxide was used as the solvent for PA6, and formic acid for PA66, and methylethylketone was used as the non-solvent for both polymers. The recycled polymers were evaluated by determination of molecular weight, crystallinity and grain size. Excellent recoveries were achieved, with no deterioration in the polymer properties. 33 refs. 

HMF is an important versatile sugar derivative and is a key intermediate between bio-based carbohydrate chemistry and petroleum based industrial organic chemistry (1, 2). The most coimnon feedstock for HMF is fructose and reactions are carried out in water-based solvent systems using acid catalysis (3,4). HMF is unstable in water at low pH and breaks down to form levulinic acid and formic acid, resulting in an expensive HMF recovery process. In strongly polar organic co-solvents, such as dimethylsulfoxide (DMSO), levuhnic acid formation is reduced and HMF yields are improved (5). 

In an industrial application dissolution/reprecipitation technology is used to separate and recover nylon from carpet waste [636]. Carpets are generally composed of three primary polymer components, namely polypropylene (backing), SBR latex (binding) and nylon (face fibres), and calcium carbonate filler. The process involves selective dissolution of nylon (typically constituting more than 50wt% of carpet polymer mass) with an 88 wt % liquid formic acid solution and recovery of nylon powder with scCC>2 antisolvent precipitation at high pressure. Papaspyrides and Kartalis [637] used dimethylsulfoxide as a solvent for PA6 and formic acid for PA6.6, and methylethylketone as the nonsolvent for both polymers. 

A gas liquid chromatographic (GLC) method was described for determining residues of Bayer 73 (2-aminoethanol salt of niclosamide) in fish muscle, aquatic invertebrates, mud, and water by analyzing for 2-chloro-4-nitroaniline, a hydrolysis product of Bayer 73 [83]. Residues were extracted with acetone-formic acid (98 + 2), and partitioned from water samples with chloroform. After sample cleanup by solvent and acid base partitioning, the concentrated extract was hydrolyzed with 2N NaOH and H202 for 10 min at 95°C. The 2-chloro-4-nitroaniline was then partitioned hexane ethyl ether (7 + 3) and determined by electron capture GLC. Average recoveries were 88% for fish, 82% for invertebrates, 82% for mud, and 98% for water at 3 or more fortification levels. 

Relative extraction efficiencies of polar polymeric neutral, cation, and anion exchange sorbents (HLB, MCX, and MAX) for 11 beta antagonists and 6 beta agonists in human whole blood were probed.109 Initial characterization of MCX and MAX for acidic and basic load conditions, respectively, showed that both the agonists and antagonists were well retained on MCX, while they were recovered from MAX in the wash with either methanol or 2% ammonia in methanol (see Table 1.6). Blood samples were treated with ethanol containing 10% zinc sulfate to precipitate proteins and the supernatants loaded in 2% aqueous ammonium hydroxide onto the sorbents. After a 30% methanol and 2% aqueous ammonia wash, the analytes were eluted with methanol (HLB), 2% ammonia in methanol (MCX), or 2% formic acid in methanol (MAX). The best recoveries were observed with MCX under aqueous conditions or blood supernatant (after protein precipitation) spiked sample load conditions (see Table 1.7). Ion suppression studies by post-column infusion showed no suppression for propranolol and terbutaline with MCX, while HLB and MAX exhibited suppression (see Figure 1.6). 

One of the major advantages of the metal oxide catalyst over that of the straight metal catalyst is the elimination of the need for a methanol recovery tower. The metal oxide catalysts result in not only high yields, but also very high conversion rates. Consequently, there is no need to recover the small amounts of methanol that remain unreacted. It becomes part of the aqueous formaldehyde solution and serves as a stabilizer for the system. By-products are CO, CO2, dimethyl ether, and formic acid. The process yields (the percent of the methanol that ends up in formaldehyde) are 95-98%. 

An unstable analogue of prostaglandin, PGE, formulated in a poly butadiene polymeric matrix, was placed in a SFE cell and extracted with C02/formic acid (95 5) at 15°C Extraction was continued for 60 min and then the extract was collected in hexane/ethanol (2 1) at 0"C. The advantages of the SFE method were that the solvent effected simultaneous cleavage of the polymer-prostaglandin bond without instability problems and with improved mass transfer enabling good recovery from the polymer matrix. 

Formic Acid Recovery After Freeze-Drying... 

Poorly soluble virus proteins have been separated by RPC through gradients of formic acid/acetonitrile. Even under these harsh conditions about 100% recovery was found 71 K... 

It has been presumed that there are two possible causes for the poor recoveries of cyst(e)ine as cysteic acid. The first is the incomplete conversion of cyst(e)ine to cysteic acid by the per-formic acid oxidation. The second is the oxidative destruction of cysteic acid during the HC1 digestion due primarily to the presence of residual performic acid at elevated temperatures. In response to this possibility, many studies have employed the addition of HBr after the oxidative pretreatment to consume excess/residual peroxide. An interesting collaborative study reported by Llames and Fontaine (84) compares the use of HBr vs. metabisulfite for the purpose of scavenging leftover peroxide. It appears the use of hydrobromic acid yields slightly better results. 

VC Mason, M Rudemo, S Bech-Andersen. Hydrolysate preparation for amino acid determinations in feed constituents. 6. The influence of phenol and formic acid on the recovery of amino acids from oxidized feed proteins. Z Tierphysiol Tierernaehr Futtermittelkd 43 35-48, 1980. 

Kim and Salem (33) found that the acidic PL were eluted from an aminopropyl bonded phase with over 95% recovery with 4 ml of a mixture of H/2-P/Ethanol/0.1 M aqueous NH4-ac-etate/formic acid (420/350/100/50/0.5) containing 5% phosphoric acid (Table 2). Neither the solvent mixture without phosphoric acid nor methanol containing 5% phosphoric acid was able to elute the acidic PL. Actually, Table 2 indicates that a fractionation of both neutral and acidic PL is enabled by the sequential elution with methanol and the aforementioned solvent mixture. In order to remove the phosphoric acid from the acidic PL fraction, it is first dried under N2 for 10 min to remove the hexane and then extracted three times with 1 ml of chloroform after the addition of 1 ml of water. 

High-performance LC was also used for determination of TBZ after its extraction from marmalades and curds with ethyl acetate (13). The use of a buffered mobile phase improved the response of the UV detector, and column performance remained constant throughout 2 months of daily use with a detection limit of 100 ppb. Three detectors (UV, fluorimetric, and electrochemical) were used for the determination of OPP, BP, and TBZ in plant materials (45). The compounds were extracted with dichloromethane and separated on an RP-18 column with a methanolic formic acid buffer as eluent. It was not possible to determine TBZ using an electrochemical detector, although the extraction recovery varied between 80 and 95%. 

Ninhydrin forms fluorophors of high intensity with guanidino compounds in alkaline media. Dihydrostreptomycin, which has two guanidino groups, yields similar fluorophors. Milk sample was treated with TCA, to precipitate proteins, and extracted with dichloromethane and NaOH, and the supernatant cleanup was performed using a Cl8 SPE column. The analyte was eluted with formic acid in MeOH. The postcolumn derivatization was performed at 80°C. The recovery from all procedures varied from 82.6% to 82.8% (only for two concentration levels), with RSD of 0.7-1.2%. This method can also be used for the determination of STR in milk (112). 

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