Material for a facility for the production of anhydrous formic acid

Abstract

The invention relates to an apparatus and a process for the preparation of anhydrous or substantially anhydrous formic acid. This apparatus is constructed partly or entirely of substantially zirconium-free materials. The extractant employed is a liquid of the general formula I 1

Description

[0001] The invention relates to an apparatus and a process for obtaining anhydrous or substantially anhydrous formic acid, and to the use of certain classes of material as construction materials for this apparatus.

[0002] EP-B 0 017 866 discloses that anhydrous or substantially anhydrous formic acid is obtained if

[0003] a) methyl formate is subjected to hydrolysis,

[0004] b) methanol and excess methyl formate are distilled off from the resultant hydrolysis mixture,

[0005] c) the bottom product from the distillation (b), which comprises formic acid and water, is extracted in a liquid-liquid extraction with an extractant which principally takes up the formic acid,

[0006] d) the resultant extract phase, comprising formic acid and some of the water, is subjected to distillation,

[0007] e) the top product obtained in this distillation, which comprises water and some of the formic acid, is fed back into the lower part of a distillation device in step (b),

[0008] f) the bottom product from distillation step (d), which predominantly comprises extractant and formic acid, is separated into anhydrous or substantially anhydrous formic acid and the extractant by distillation, and

[0009] g) the extractant leaving step (f) is fed back into the process.

[0010] To carry out this process, an apparatus is then provided which comprises the following elements:

[0011] a synthesis reactor for the preparation of methyl formate,

[0012] a hydrolysis reactor for the hydrolysis of methyl formate,

[0013] a distillation device for the separation of excess methanol and excess methyl formate from the hydrolysis mixture (step b)),

[0014] a distillation device for the distillation of an extract phase comprising formic acid, extractant and some of the water (step d)),

[0015] an extraction device for carrying out step c), and

[0016] a distillation device for the distillative separation of a mixture comprising predominantly extractant and formic acid into anhydrous or substantially anhydrous formic acid and extractant (step f)).

[0017] It is vital that the corresponding elements of the apparatus which come into contact with formic acid must be constructed of materials which are corrosion-resistant. Formic acid, in particular aqueous formic acid, is an extremely corrosive material. The term “corrosion” is taken to mean the interaction of a material with its environment which causes a measurable change in the material and results in an impairment of the function of the corresponding component or of the entire system. The term “corrosion” is thus taken to mean the disadvantageous and quality-reducing change in a material starting from the surface and caused by unintended chemical or electrochemical attacks. The attacking agent, which acts chemically or electrochemically, is known as a corrosive agent—formic acid, in particular aqueous formic acid, is regarded as a highly corrosive agent.

[0018] Plants for the preparation of formic acid or aqueous formic acid must therefore be protected against corrosion to a particular extent. Only a few materials are suitable as construction material for the plant parts which come into contact with formic acid. In the literature [T.-L. Yau, K. W. Bird, Chemical Engineering Process, January 1992, page 65], [T.-L. Yau, K. W. Bird, Chemical Engineering Process, January 1995, page 42], [Company Information: “Outlook”, Teledyne Vah Chang Albany, Winter/Spring 1990 Volume 11, No. 1, pages 1-3] exclusively zirconium and zirconium alloys containing at least 90% of zirconium are recommended as materials for this purpose. On contact with formic acid, zirconium is passivated—forms a stable oxidic protective layer. Other materials are less suitable, or suitable materials (apart from zirconium) are so expensive that they cannot be employed economically. Thus, industrial plant parts which come into contact with formic acid are generally made exclusively of zirconium or zirconium alloys containing at least 90% of zirconium. It is disadvantageous that zirconium-rich materials are expensive, and the investment costs of corresponding plant parts are therefore high.

[0019] It is an object of the present invention to provide an apparatus with which the above-mentioned process for the preparation of anhydrous or substantially anhydrous formic acid can be carried out. The material costs for the construction of the apparatus in question should be lower than comparatively for a corresponding apparatus constructed of zirconium-rich materials.

[0020] We have found that this object is achieved by an apparatus for obtaining anhydrous or substantially anhydrous formic acid, comprising

[0021] i) a synthesis reactor for the preparation of methyl formate,

[0022] ii) a hydrolysis reactor for the hydrolysis of methyl formate,

[0023] iii) a distillation device for the separation of excess methanol and excess methyl formate from the hydrolysis mixture,

[0024] iv) a distillation device for the distillation of an extract phase comprising formic acid, extractant and some of the water,

[0025] v) an extraction device, and

[0026] vi) a distillation device for the distillative separation of a mixture comprising predominantly extractant and formic acid into anhydrous or substantially anhydrous formic acid and extractant,

[0027] where the extractant employed is a carboxamide of the general formula I 2

[0028] where the radicals R1 and R2 are alkyl, cycloalkyl, aryl or aralkyl groups, or R1 and R2 jointly, together with the N atom, form a heterocyclic 5- or 6-membered ring, and only one of the radicals is an aryl group, and where R3 is hydrogen or a C1-C4-alkyl group.

[0029] Thus, the apparatus according to the invention is characterized in that the devices ii), iii), iv), v) and/or vi) are constructed partly or entirely of a low-zirconium material selected from the group consisting of the material classes titanium/palladium alloys, chromium-, molybdenum- and/or tungsten-containing nickel-based materials and molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels. The term “low-zirconium material” is taken to mean a material which contains less than 10% by weight, preferably less than 1% by weight, of zirconium.

[0030] Examples for chromium-, molybdenum- and/or tungsten-containing nickel-based materials are materials containing 14 to 24% by weight of Cr, 8 to 17% by weight of Mo and/or 3 to 5% by weight of W, max. 25% by weight of other elements and Ni as rest.

[0031] Examples for molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels are steels containing 18 to 30% by weight of Cr, 12 to 40% by weight of Ni, 3 to 7% by weight of Mo, max. 3% by weight of Cu, max. 0.05% by weight of C, max. 25% by weight of other elements and Fe as rest.

[0032] These both groups of material are essential for the invention.

[0033] Examples for titanium/palladium alloys are alloys containing 0.1 to 0.25% by weight of Pd, max. 0.4% by weight of oxygen, max. 0.5% by weight of Fe, max. 1% by weight of any other element and Ti as rest. The total amount of all other elements—conventional additives, which are added during preparation of the alloys, and impurities—is max. 2% by weight related to the total composition of the alloy. In this kind of material class titanium/palladium alloys of this constitution are preferred.

[0034] If said alloys have counterparts with a different name, these are also included if they have a comparable composition and properties.

[0035] The term “substantially anhydrous formic acid” is taken to mean formic acid which contains a maximum of 30% by weight, preferably a maximum of 15% by weight, of water. The term “synthesis reactor” is taken to mean a device in which firstly the synthesis of methyl formate is carried out (usually in a corresponding reactor) and secondly, if desired, separation of the resultant synthesis mixture is carried out (usually in a distillation device downstream of the reactor). Suitable hydrolysis reactors are any desired reactors which can be employed for the hydrolysis of methyl formate. The extraction device employed is preferably a liquid-liquid extraction column. Suitable distillation devices are, in particular, distillation columns.

[0036] In the tables below, suitable classes of material (classes I to III) are defined in detail. The term “other elements” is taken to mean selectively added other elements as well as conventional additives, which are added during preparation, and impurities.

TABLE 1
Class I	Class II	Class III
Titanium/	Chromium-, molybdenum-	Molybdenum-containing,
palladium alloys	and/or tungsten-containing	highly alloyed, austenitic
	nickel-based materials	chromium/nickel special
		steels

[0037]

TABLE 2
	Class I
	Titanium/palladium alloys
Characteristic	Palladium: 0.1-0.25% by weight
alloy	Oxygen: max. 0.4% by weight
composition	Iron: max. 0.5% by weight
(principal	Other elements: each max. 1% by weight,
elements)	total max. 2% by weight;
	corresponding to the materials/standards mentioned
	below Rest (basis material): titanium
		Abbreviated
Examples	Country	name	Material No.	Standard
	D	Ti1Pd	3.7225	DIN 17851
		Ti2Pd	3.7235	DIN 17851
		Ti3Pd	3.7255	DIN 17851
	USA	TiPd grade 7	UNS R52400	ASTM
				B265,
				B337, B338,
				B348, B381
		TiPd grade 11	UNS R52250	ASTM
				B265,
				B337, B338,
				B348, B381

[0038]

TABLE 3
	Class II
	Chromium-, molybdenum- and/or tungsten-containing nickel-based materials
Characteristic	Chromium: 14-24% by weight
alloy	Molybdenum: 8-17% by weight and/or tungsten: 3-5% by weight
composition	Other elements: each max. 10% by weight, total max. 25% by weight; for examples see below
(principal	Rest (basis material): nickel
elements)
Examples	Country	Abbreviated name	Material No.	Standard
	D	NiMo16Cr15W	2.4819	DIN 17744
	USA	Alloy C-276	UNS N10276	ASTM B366, B564, B574, B575,
				B619, B622, B626
	D	NiCr22Mo9Nb	2.4856	DIN 17744, EN 10095
	USA	Alloy 625	UNS N06625	ASTM B366, B443, B444, B446, B704, B705
	D	NiMo16Cr16Ti	2.4610	DIN 17744
	USA	Alloy-C4	UNS N06455	ASTM B574, B575, B619, B622, B626
	D	NiCr23Mo16Al	2.4605	VdTUV materials sheet 505
	USA	Alloy 59	UNS N06059	ASTM B622, B619, B626, B575, B574, B564
	D	NiCr21Mo16W	2.4606	VdTUV materials sheet 515
	USA	Alloy 686	UNS N06686	ASTM B564, B574, B575, B619, B622, B626
	D	NiCr23Mo16Cu	2.4606	not yet standardized
	USA	Alloy C2000		not yet standardized
		(Hastelloy ®
		C-2000 ®
		alloy)

[0039]

TABLE 4
	Class III
	Molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels
Characteristic	Chromium: 18-30% by weight
alloy	Nickel: 12-40% by weight
composition	Molybdenum: 3-7% by weight
(principal	Copper: max. 3% by weight
elements)	Carbon: max. 0.05% by weight
	Other elements: each max. 10% by weight,
	total max. 25% by weight; for examples see below
	Rest (basis material): iron
Examples	Country	Abbreviated name	Material No.	Standard
	D	X2NiCrMoN	1.4439	EN 10088-1-2-3, DIN 17440, DIN 17441
		17-13-5
	D	X1NiCrMoCuN	1.4529	EN 10088-1-2-3
		25-20-7
	D	X1NiCrMoCu	1.4539	EN 10088-1-2-3
		25-20-5
	USA		UNS N08904	ASTM A240, A480, B625, B649,
				B673, B674, B677
	D	X1CrNiMoCuN	1.4547	EN 10088-1-2-3
		20-18-7
	USA		UNS S31254	ASTM A182, A193, A194, A204,
				A249, A269,
				A276, A312, A358, A403, A409, A479,
				A813, A814
	USA		UNS S31725	ASTM A167, A182, A213,
				A240, A249, A269,
				A276, A312, A358, A376, A409, A479
	USA		UNS S31726	ASTM A167, A182, A213,
				A240, A249, A269,
				A276, A312, A358, A376, A409, A479
Precise concentration data for examples from the three classes of material indicated

[0040]

TABLE 5
Class 1: Material number 3.7235
Chemical composition in % by weight
	Others
							Indi-
							vidu-	Togeth-
	Fe	O	N	C	H	Pd	ally	er	Ti
Min						0.15			Basis
Max	0.20	0.18	0.05	0.06	0.013	0.25	0.1	0.4	Basis

[0041]

TABLE 6
Class 2: Material number 2.4819
Chemical composition in % by weight
	Others
	(V, Cu, W, Fe etc.)
	C	Si	Mn	P	S	Co	Cr	Mo	Individually	Together	Ni
Min							14.5	15.0			Basis
Max	0.015	0.08	1.0	0.025	0.015	2.5	16.5	17.0	7.0	13.0

[0042]

TABLE 7
Class 2: Material number 2.4856
Chemical composition in % by weight
	Others (Cu, Nb, Ti, Fe etc.)
	C	Si	Mn	P	S	Al	Co	Cr	Mo	Individually	Together	Ni
Min	0.03							20.0	8.0			Basis
												(58.0)
Max	0.10	0.5	0.5	0.020	0.015	0.40	1.0	23.0	10.0	5.0	10.0

[0043]

TABLE 8
Class 3: Material number 1.4439
Chemical composition in % by weight
	C	Si	Mn	P	S	N	Cr	Mo	Ni	Fe
Min						0.12	16.5	4.0	12.5	Basis
Max	0.030	1.0	2.0	0.045	0.015	0.22	18.5	5.0	14.5

[0044] The extractant employed acts as corrosion inhibitor on contact of the above mentioned classes of material with aqueous formic acid.

[0045] The low-zirconium classes of material which are suitable are significantly cheaper than the materials recommended in the prior art, which have a high content of zirconium. The construction costs of an apparatus according to the invention for the preparation of anhydrous or substantially anhydrous formic acid are thus comparatively favorable.

[0046] In general, at least the surfaces of devices ii), iii), iv), v) and/or vi) which come into contact with formic acid and the extractant are constructed of the low-zirconium material—the term “surface” in this connection is taken to mean an external thin layer, preferably with a thickness of about 1 mm.

[0047] Said surfaces usually come into contact with media containing at least 1% of formic acid and at least 1%, preferably 5%, of extractant.

[0048] In the plant parts which are constructed partly or completely of the above mentioned low-zirconium materials, temperatures of up to a maximum of about 190° C. and pressures of up to a maximum of about 3 bar are reached. Even under these high temperatures and pressures, these materials are suitable as construction material in the presence of the extractant.

[0049] In a preferred embodiment of the invention, devices iii) and iv) are arranged in a single distillation device. The latter is generally in the form of a column.

[0050] Preferred extractants are N,N-di-n-butylformamide, N,N-di-n-butylacetamide, N-methyl-N-2-heptylformamide, N-n-butyl-N-2-ethylhexylformamide, N-n-butyl-N-cyclohexylformamide and/or N-ethylformanilide.

[0051] The invention also relates to the use of a low-zirconium material selected from the group consisting of the material classes titanium/palladium alloys, chromium-, molybdenum- and/or tungsten-containing nickel-based materials and molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels, as construction material for the above-described apparatus.

[0052] The invention also relates to a process for obtaining anhydrous or substantially anhydrous formic acid based on a process in which, in a plant,

[0053] α) methyl formate is subjected to hydrolysis,

[0054] β) methanol and excess methyl formate are distilled off from the resultant hydrolysis mixture,

[0055] χ) the bottom product from distillation β), comprising formic acid and water, is extracted in a liquid-liquid extraction with an extractant which principally takes up the formic acid, and the extractant employed here is a carboxamide of the general formula I 3

[0056] where the radicals R1 and R2 are alkyl, cycloalkyl, aryl or aralkyl groups, or R1 and R2 jointly, together with the N atom, form a heterocyclic 5- or 6-membered ring, and only one of the radicals is an aryl group, and where R3 is hydrogen or a C1-C4-alkyl group,

[0057] δ) the resultant extract phase, comprising formic acid, extractant and some of the water, is subjected to distillation,

[0058] ε) the top product obtained in this distillation, which comprises water and some of the formic acid, is fed back into the lower part of the distillation device in step β),

[0059] φ)) the bottom product from distillation step δ), which comprises predominantly extractant and formic acid, is separated by distillation into anhydrous or substantially anhydrous formic acid and the extractant, and

[0060] γ) the extractant leaving step φ) is fed back into the process.

[0061] Thus, the process according to the invention is characterized in that one or more plant parts which come into contact with formic acid and with extractant are constructed partly or completely of a low-zirconium material selected from the group consisting of the material classes titanium/palladium alloys, chromium-, molybdenum- and/or tungsten-containing nickel-based materials and molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels.

[0062] The temperatures during the process are on average, that means on average during all steps α) to γ) 75° C., preferably 85° C., most preferably 100° C. Especially the average temperature per step α) to γ) is in general 75° C., preferably 85° C., most preferably 100° C.

[0063] In general, the plant parts which come into contact with formic acid and with extractant are in the form of the reactor for carrying out step α), the distillation device for carrying out step β), the distillation device for carrying out step δ), the extractant device for carrying out step χ) and/or the distillation device for carrying out step φ). The extractant employed is usually N,N-di-n-butylformamide, N,N-di-n-butylacetamide, N-methyl-N-2-heptylformamide, N-n-butyl-N-2-ethyl-hexylformamide, N-n-butyl-N-cyclohexylformamide and/or N-ethylformanilide.

[0064] The attached drawing shows

[0065] in FIG. 1 a diagram of a plant for the preparation of anhydrous or substantially anhydrous formic acid,

[0066] in FIG. 2 a diagram of a plant for the preparation of anhydrous or substantially anhydrous formic acid, with the distillation device for carrying out step β) and the distillation device for carrying out step δ) are arranged in a single distillation device.

[0067] The reference numerals entered above, below or alongside the arrows indicate the components which generally have a high proportion or the principal proportion in the respective streams. Since the proportions of the components in the streams can vary, these reference numerals should only serve as guide values for information. Reference numeral 21 denotes methyl formate, 22 denotes water, 23 denotes formic acid, 24 denotes methanol, 25 denotes extractant and 27 denotes carbon monoxide. It is shown that methyl formate is prepared in a synthesis reactor 6, the hydrolysis of the methyl formate is carried out in a hydrolysis reactor 1, and step β) is carried out in a distillation device 2, the extraction is carried out in an extraction device 3, step δ) is carried out in a distillation device 4, and step φ) is carried out in a distillation device 5.

[0068] In FIG. 2, the distillation devices 2; 4 are arranged in a single distillation device 7.

[0069] The present invention will be explained in greater detail below with reference to a working example.

EXAMPLE

[0070] The extractant/anticorrosion agent employed is N,N-di-n-butylformamide. The materials studied are exposed to the corrosive medium in an autoclave. The system pressure is 3 bar, and the sample residence time is 10 days. The corresponding materials are studied with respect to their stability in seven different media. The temperatures and compositions of the mixtures indicate approximately the conditions prevailing in the process in the preparation of anhydrous or substantially anhydrous formic acid. The experimental conditions are shown in the table below.

TABLE 9a
					Mixture 5	Mixture 6
					(concen-	(concen-
			Mixture 3	Mixture 4	trated FA in	trated FA in
	Mixture 1	Mixture 2	(aqueous	(organic	DBF, high	DBF, moder-
	(aqueous	(organic	phase with a	phase with a	temper-	ate tempera-	Mixture 7
Components	phase)	phase)	little FA)	little FA)	ature)	ture)	(no DBF)
FA, % by wt.	20	16	5	5	12	12	85
DBF, % by wt.	2	72	2	83	87	87	—
W, % by wt.	78	12	93	12	1	1	15
Temperature, ° C.	110	110	110	110	160	80	150
FA = formic acid,
DBF = N,N-di-n-butylformamide,
W = water

[0071] The corrosion studies give the following results:

	TABLE 9b
	Mixture
Material No.	1	2	3	4	5	6	7
Class I: 3.7235 (DIN 17851)	+	+	+	+	+	+	−
Class II: 2.4856 (DIN 17744,	+	+	+	+	−	+	−
EN 10095) and 2.4819 (DIN 17744)
Class III: 1.4439	−	−	+	+	−	+	−
(EN 10088-1-2-3, DIN 17440,
DIN 17441)
In the above table, a material is regarded as resistant (+) if it has a corrosion rate of less than 0.1 mm/year - otherwise, the material is denoted by (−).

[0072] The results shown in the above table indicate that materials from all three classes I to III are resistant in mixtures according to the invention containing extractants/anticorrosion agents and aqueous formic acid. It is also clear that without the use of the extractant/anticorrosion agent, the materials tested are less suitable.

Claims

1. An apparatus for obtaining anhydrous or substantially anhydrous formic acid, comprising i) a synthesis reactor (6) for the preparation of methyl formate, ii) a hydrolysis reactor (1) for the hydrolysis of methyl formate, iii) a distillation device (2) for the separation of excess methanol and excess methyl formate from the hydrolysis mixture, iv) a distillation device (4) for the distillation of an extract phase comprising formic acid, extractant and some of the water, v) an extraction device (3), and vi) a distillation device (5) for the distillative separation of a mixture comprising predominantly extractant and formic acid into anhydrous or substantially anhydrous formic acid and extractant, where the extractant employed is a carboxamide of the general formula I 4where the radicals R1 and R2 are alkyl, cycloalkyl, aryl or aralkyl groups, or R1 and R2 jointly, together with the N atom, form a heterocyclic 5- or 6-membered ring, and only one of the radicals is an aryl group, and where R3 is hydrogen or a C1-C4-alkyl group, characterized in that the devices ii) (1), iii) (2), iv) (4), v) (3) and/or vi) (5) are constructed partly or entirely of a low-zirconium material selected from the group consisting of the material classes titanium/palladium alloys, chromium-, molybdenum- and/or tungsten-containing nickel-based materials and molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels, where the chromium-, molybdenum- and/or tungsten-containing nickel-based materials contain 14 to 24% by weight of Cr, 8 to 17% by weight of Mo and/or 3 to 5% by weight of W, max. 25% by weight of other elements and Ni as rest, and the molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels contain 18 to 30% by weight of Cr, 12 to 40% by weight of Ni, 3 to 7% by weight of Mo, max. 3% by weight of Cu, max. 0.05% by weight of C, max. 25% by weight of other elements and Fe as rest.

2. An apparatus as claimed in claim 1, wherein surfaces of devices iv) (4), v) (3) and/or vi) (5) which come into contact with formic acid and the extractant are constructed of the low-zirconium material.

3. An apparatus as claimed in claim 2, wherein the surfaces come into contact with media which contain at least 1% of formic acid and at least 1%, preferably 5%, of extractant.

4. An apparatus as claimed in one of claims 1 to 3, wherein devices iii) (2) and iv) (4) are arranged in a single distillation device (7).

5. An apparatus as claimed in one of claims 1 to 4, wherein the extractant employed is N,N-di-n-butylformamide, N-di-n-butylacetamide, N-methyl-N-2-heptylformamide, N-n-butyl-N-2-ethylhexylformamide, N-n-butyl-N-cyclohexylformamide and/or N-ethylformanilide.

6. The use of a low-zirconium material selected from the group consisting of the material classes titanium/palladium alloys, chromium-, molybdenum-and/or tungsten-containing nickel-based materials and molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels, as construction material for an apparatus as claimed in one of claims 1 to 5, where the chromium-, molybdenum- and/or tungsten-containing nickel-based materials contain 14 to 24% by weight of Cr, 8 to 17% by weight of Mo and/or 3 to 5% by weight of W, max. 25% by weight of other elements and Ni as rest, and the molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels contain 18 to 30% by weight of Cr, 12 to 40% by weight of Ni, 3 to 7% by weight of Mo, max. 3% by weight of Cu, max. 0.05% by weight of C, max. 25% by weight of other elements and Fe as rest.

7. A process for obtaining anhydrous or substantially anhydrous formic acid, in which, in a plant, α) methyl formate is subjected to hydrolysis, β) methanol and excess methyl formate are distilled off from the resultant hydrolysis mixture, χ) the bottom product from distillation β), comprising formic acid and water, is extracted in a liquid-liquid extraction with an extractant which principally takes up the formic acid, and the extractant employed here is a carboxamide of the general formula I 5 where the radicals R1 and R2 are alkyl, cycloalkyl, aryl or aralkyl groups, or R1 and R2 jointly, together with the N atom, form a heterocyclic 5- or 6-membered ring, and only one of the radicals is an aryl group, and where R3 is hydrogen or a C1-C4-alkyl group, δ) the resultant extract phase, comprising formic acid, extractant and some of the water, is subjected to distillation, ε) the top product obtained in this distillation, which comprises water and some of the formic acid, is fed back into the lower part of the distillation device in step β), 100 ) the bottom product from distillation step ε), which comprises predominantly extractant and formic acid, is separated by distillation into anhydrous or substantially anhydrous formic acid and the extractant, and γ) the extractant leaving step φ) is fed back into the process, characterized in that one or more plant parts which come into contact with formic acid and with extractant are constructed partly or completely of a low-zirconium material selected from the group consisting of the material classes titanium/palladium alloys, chromium-, molybdenum- and/or tungsten-containing nickel-based materials and molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels, where the chromium-, molybdenum- and/or tungsten-containing nickel-based materials contain 14 to 24% by weight of Cr, 8 to 17% by weight of Mo and/or 3 to 5% by weight of W, max. 25% by weight of other elements and Ni as rest, the molybdenum-containing, highly alloyed, austenitic chromium/nickel special steels contain 18 to 30% by weight of Cr, 12 to 40% by weight of Ni, 3 to 7% by weight of Mo, max. 3% by weight of Cu, max. 0.05% by weight of C, max. 25% by weight of other elements and Fe as rest, and the temperatures during the process are on average 75° C.

8. A process as claimed in claim 7, wherein the plant parts which come into contact with formic acid and with extractant are in the form of the reactor for carrying out step α), the distillation device for carrying out step β), the distillation device for carrying out step δ), the extraction device for carrying out step χ) and/or the distillation device for carrying out step φ).

9. A process as claimed in claim 7 or 8, wherein the extractant employed is N,N-di-n-butylformamide, N,N-di-n-butylacetamide, N-methyl-N-2-heptyl-formadine, N-n-butyl-N-2-ethylhexylformamide, N-n-butyl-N-cyclohexylformamide and/or N-ethylformanilide.