EP2984037A1 - Procédé de synthèse d'acide cyanhydrique à partir de formamide en présence d'un catalyseur - Google Patents

Procédé de synthèse d'acide cyanhydrique à partir de formamide en présence d'un catalyseur

Info

Publication number
EP2984037A1
EP2984037A1 EP14718544.1A EP14718544A EP2984037A1 EP 2984037 A1 EP2984037 A1 EP 2984037A1 EP 14718544 A EP14718544 A EP 14718544A EP 2984037 A1 EP2984037 A1 EP 2984037A1
Authority
EP
European Patent Office
Prior art keywords
formamide
thermolysis
catalyst
reactor
gaseous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14718544.1A
Other languages
German (de)
English (en)
Inventor
Ralf Böhling
Michael Schipper
Jens Bernnat
Wilhelm Weber
Peter Petersen
Anton Negele
Andreas Deckers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP14718544.1A priority Critical patent/EP2984037A1/fr
Publication of EP2984037A1 publication Critical patent/EP2984037A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/02—Preparation, separation or purification of hydrogen cyanide
    • C01C3/0204—Preparation, separation or purification of hydrogen cyanide from formamide or from ammonium formate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g

Definitions

  • the present invention relates to a process for the preparation of hydrocyanic acid by thermolysis of gaseous formamide in the presence of an alumina catalyst having a BET surface area of ⁇ 1 m 2 / g in a reactor having an inner surface which is inert with respect to the thermolysis of formamide and the use of the alumina catalyst in a process for the production of hydrogen cyanide by thermolysis of gaseous formamide.
  • Hydrocyanic acid is an important basic chemical that can be used as a starting material for. B. in numerous organic syntheses, such as the production of adiponitrile, methacrylic acid esters, methionine and complexing agents (NTA, EDTA) is used. In addition, hydrocyanic acid is required for the production of alkali cyanides used in the mining and metallurgical industries.
  • DE 498 733 relates to a process for the preparation of hydrogen cyanide from formamide by catalytic dehydration in which the catalyst used is a dehydrating catalyst such as alumina, thoria or zirconia, the catalyst being annealed for a long time before use for a substantial reduction in activity becomes.
  • the catalyst used is a dehydrating catalyst such as alumina, thoria or zirconia
  • hydrocyanic acid is obtained in yields of between 30.6 and 91.5%.
  • DE 498 733 contains no information.
  • DE 498 733 gives no information regarding the selectivity of the catalyst used.
  • DE 199 62 418 A1 discloses a continuous process for producing hydrogen cyanide by thermolysis of gaseous, superheated formamide at elevated temperature and reduced pressure. The process is conducted in the presence of a particulate solid catalyst in a thermolysis reactor wherein the solid catalyst is kept in motion by a vertically upwardly or vertically-downwardly directed flow of the gaseous reaction mixture.
  • the catalysts used according to DE 199 62 418 A1 are alumina or alumina / silica catalysts.
  • DE 199 62 418 A1 contains no information.
  • DE 199 62 418 A1 likewise does not disclose any information regarding the selectivity of the method described in DE 199 62 418 A1.
  • EP 0 209 039 A2 relates to a process for the thermolytic cleavage of formamide to blue acid and water on highly sintered alumina or alumina-silica moldings or on high-temperature corrosion-resistant stainless steel packings in the simultaneous presence of atmospheric oxygen.
  • EP 0 209 039 A2 uses stainless steel or iron pipes.
  • highly sintered aluminosilicate is used as the catalyst.
  • a conversion of 98 to 98.6% and a selectivity of 95.9 to 96.7% are achieved in the thermolysis of formamide.
  • the hydrocyanic crude gas mixture produced according to the processes of the prior art has CO, NH 3 and CO 2 components as a result of side reactions and therefore has to be purified.
  • the object of the present application over the prior art is therefore to avoid a purification of the crude acid gas mixture obtained by thermolysis of formamide and to use the crude hydrocyanic acid directly in subsequent stages.
  • the direct use of the hydrocyanic crude gas obtained in subsequent stages avoids the handling of liquid blue-acid which, in the presence of traces of basic components such as NH3, tends to give rise to explosive reactions.
  • the object is achieved by a process for the preparation of hydrogen cyanide by thermolysis of gaseous formamide in a reactor in the presence of a catalyst, wherein a) the catalyst
  • the reactor has an inner surface which is inert with respect to the thermolysis of formamide.
  • the contact of the gaseous formamide with iron or iron-containing materials / compounds, such as steel, is avoided during the thermolysis of the gaseous formamide.
  • extremely high selectivity of blue acid can be achieved, which make purification of the crude hydrocyanic acid obtained superfluous.
  • An inner surface of the reactor means the surface which reacts with the reactants, i. H. inter alia with the gaseous formamide, is in direct contact.
  • Suitable inner surfaces of the reactor which are inert with respect to the thermolysis of formamide, are preferably selected from silicon-coated steel surfaces and quartz glass. Also suitable are, for example, titanium, SiC and zirconium.
  • the catalyst used in the process according to the invention is an alumina catalyst comprising
  • the aluminum oxide catalyst used according to the invention is characterized in that it has a BET surface area, measured in accordance with DINISO 9277: 2003-05, of ⁇ 1 m 2 / g, preferably 0.01 to 0.9 m 2 / g, particularly preferably 0 , 02 to 0.3 m 2 / g.
  • the aluminum oxide catalyst used according to the invention can be based on commercially available catalysts (eg aluminum oxide chippings from Feuerfest) by heat treatment of these catalysts at> 1400 ° C. for 1 to 30 h, preferably> 1500 ° C. for 1 to 30 h preferably at 1500 ° C to 1800 ° C for 2 to 10 hours, or can be prepared according to methods known to those skilled in the art.
  • commercially available catalysts eg aluminum oxide chippings from Feuerfest
  • Essential for achieving a high selectivity is the tempering of the alumina catalyst at> 1400 ° C for 1 to 30 h, preferably> 1500 ° C for 1 to 30 h, more preferably at 1500 ° C to 1800 ° C for 2 to 10 h ,
  • the aluminum oxide catalyst used according to the invention can be prepared by pressing freshly precipitated aluminum hydroxide or corresponding mixtures with silica gel after slight drying into the desired moldings and then at temperatures> 1400 ° C. for 1 to 30 h, preferably> 1500 ° C for 1 to 30 h, more preferably at 1500 ° C to 1800 ° C for 2 to 10 h tempered.
  • the catalyst is present in the process according to the invention generally in the form of shaped bodies selected from ordered moldings and disordered moldings. Suitable moldings are z. As grit, Raschig rings, Pall rings, tablets, balls and similar moldings. It is essential that beds of moldings used allow for moderate heat losses a good heat transfer. The size or geometry of the moldings used depends on the inner diameter of the reactor used.
  • Suitable sizes are z. B. average diameter of the moldings, z. B. grit, of generally 0.1 to 10 mm, preferably 0.5 to 5 mm, particularly preferably 0.7 to 3 mm.
  • the amount of catalyst used is generally 2 to 0.1 kg, preferably 1 to 0.2 kg, based on a continuous flow of formamide of 1 kg per h.
  • suitable reactors are known in the art.
  • Preferred reactors for the thermolysis of gaseous formamide for the production of hydrogen cyanide are tubular reactors, more preferably multi-tubular reactors, for. B. Rohrbündelapparate or similar apparatus that bring the heat of reaction over the entire reaction path.
  • horde apparatuses or fluidized bed apparatuses are also suitable, with suitable horde apparatuses, fluidized bed apparatuses and tube bundle apparatuses being known to the person skilled in the art.
  • the reaction channels of the reactor used preferably tubular reactor, generally have hydraulic diameters of 0.5 mm to 100 mm, preferably 1 mm to 50 mm, particularly preferably 3 mm to 10 mm.
  • hydraulic diameter means the mean hydraulic diameter, which in each case relates to a reactor used in accordance with the present application, preferably a tubular reactor.
  • the hydraulic diameter ie, a theoretical quantity, can be used to perform calculations on pipes or channels of non-circular cross-section.
  • thermolysis of gaseous formamide to produce hydrocyanic acid is carried out in the process according to the invention at a temperature of 350 to 700 ° C, preferably 380 to 650 ° C, particularly preferably 440 to 620 ° C. If higher temperatures above 700 ° C are used, the selectivities worsen.
  • the pressure in the process according to the invention is generally from 70 mbar to 5 bar, preferably from 100 mbar to 4 bar, particularly preferably from 300 mbar to 3 bar, very particularly preferably from 600 mbar to 1.5 bar absolute pressure.
  • the thermolysis of gaseous formamide is preferably carried out in the process according to the invention in the presence of oxygen, preferably air-oxygen.
  • oxygen preferably air-oxygen.
  • the amounts of oxygen, preferably air-oxygen are generally> 0 to 10 mol%, based on the amount of formamide used, preferably 0.1 to 9 mol%, particularly preferably 0.5 to 3 mol%.
  • a driving without the addition of oxygen is possible, for. B. with a cyclic burnup of the deposits formed in the thermolysis reactor.
  • the optimum catalyst loading in the process according to the invention results from the desired degree of conversion and the size of the moldings used.
  • the catalyst loading is at a target conversion of e.g. > 90% at about 1 to 2 g of formamide per g of catalyst per hour, at a temperature of 550 ° C.
  • the heating of the reactor used in the process according to the invention is generally carried out with hot burner exhaust gases (rolling gas) or by means of molten salt or direct electrical heating.
  • hot burner exhaust gases rolling gas
  • molten salt or direct electrical heating
  • the resulting residual gas from the hydrocyanic acid synthesis can be used. This generally contains CO, H2, N2 and small amounts of hydrogen cyanide.
  • gaseous formamide used in the process according to the invention is obtained by evaporation of liquid formamide.
  • Suitable processes for vaporizing liquid formamide are known to those skilled in the art and described in the state of the art mentioned in the introduction to the description.
  • the evaporation of the formamide is carried out at a temperature of 1 10 to 270 ° C.
  • the evaporation of the liquid formamide in an evaporator at temperatures of 140 to 250 ° C, more preferably 200 to 230 ° C.
  • the evaporation of the formamide is generally carried out at a pressure of 20 mbar to 3 bar.
  • the evaporation of the liquid formamide is carried out at 80 mbar to 2 bar, more preferably 600 mbar to 1, 3 bar absolute pressure.
  • the evaporation of the liquid formamide is carried out at short residence times. Very particularly preferred residence times are ⁇ 20 s, preferably ⁇ 10 s, in each case based on the liquid formamide. Due to the very short residence times in the evaporator, the formamide can be evaporated almost completely without by-product formation.
  • the abovementioned short residence times of the formamide in the evaporator are preferably achieved in milli or microstructured apparatuses. Suitable milli- or microstructured apparatuses which can be used as evaporators are, for. In DE-A-101 32 370,
  • the gaseous formamide used is thus obtained by evaporation of liquid formamide at temperatures of 100 to 300 ° C, wherein a milli or microstructured apparatus is used as the evaporator. Suitable milli-microstructured or microstructured apparatuses are described in the above-mentioned documents.
  • the main reactor used for thermolysis of formamide can be followed by a post-reactor.
  • the formamide conversion is generally up to about 98% of the equilibrium conversion (formamide full conversion), preferably> 99%, particularly preferably about 99.5, without introduction of additional heat increased% of equilibrium turnover.
  • the sheet thickness of the internals is preferably> 1 mm. Too thin sheets become ductile due to the reaction conditions and lose their stability.
  • Suitable static mixers are z. As described in DE-A-101 38 553.
  • the steel in the ordered packings of the postreactor preferably the static mixers, more preferably the static mixers made of sheets, is preferably selected from steel grades according to the standards 1 .4541, 1.4571, 1 .4573, 1.4580, 1.4401, 1 .4404, 1 .4435, 1.4816, 1 .3401, 1 .4876 and 1 .4828, particularly preferably selected from steel grades according to the standards 1.4541, 1.4571, 1.4828, 1.3401, 1.4876 and 1.4762, very particularly preferably from steel Qualities according to standards 1 .4541, 1.4571, 1.4762 and 1 .4828.
  • the gaseous reaction product obtained in the thermolysis of the formamide is usually introduced at an inlet temperature of 450 to 700 ° C in the secondary reactor.
  • the postreactor is operated at the pressure of the main reactor reduced by the pressure loss.
  • the pressure loss is e.g. 5-50 mbar.
  • oxygen preferably air-oxygen
  • a driving without the addition of oxygen is possible, for. B. with a cyclic burnup of the deposits formed in the post reactor.
  • the crude hydrogen cyanide gas obtained after thermolysis of the formamide can thus usually be quenched directly in an NH 3 absorber or, if NH 3 does not disturb the subsequent process, be used directly for further processing, e.g. for the preparation of aqueous NaCN solution or aqueous CaCN 2 solution.
  • Quenching of the Hydrocyanic Crude Typically, the quenching of the hot, after the thermolysis of gaseous formamide obtained hydrocyanic gas-containing crude gas stream with the aid of dilute acid, preferably with the aid of dilute H2SQ4 solution. This is usually in circulation pumped a quench column. Suitable quench columns are known to the person skilled in the art. At the same time, the resulting NH3 is bound to ammonium sulfate.
  • the heat gas cooling, neutralization and dilution
  • the quench column may follow a compressor which compresses the gas leaving the quench column overhead to a pressure which corresponds to a desired process for the further processing of the hydrocyanic acid gas stream.
  • it may, for. B. be a workup to pure hydrogen cyanide or any other reactions of the hydrocyanic gas stream.
  • the hydrocyanic crude gas obtained after thermolysis of the gaseous formamide can also without reaction gas quench and NH3 absorber can be used directly in the subsequent stages (process for the further processing of the hydrocyanic acid gas stream).
  • Another object of the present invention is the use of a catalyst, the
  • (ii) has a BET surface area measured in accordance with DINISO 9277: 2003-05 of ⁇ 1 m 2 / g, and (iii) at temperatures of> 1400 ° C for 1 to 30 h, preferably> 1500 ° C for 1 to 30 h, more preferably annealed at 1500 ° C to 1800 ° C for 2 to 10 h, in a process for the preparation of hydrogen cyanide by thermolysis of gaseous formamide in a reactor having an internal surface which is inert with respect to the thermolysis of formamide.
  • Examples 1 to 6 The investigations in Examples 1 to 6 are carried out in a 17 cm long electrically heated quartz glass reactor with an inner diameter of 17 mm and approximately 130 mbar reactor inlet pressure.
  • the chippingsize is about 1 to 2 mm.
  • Quartz chippings BET surface area 0.06 m 2 / g, amount of catalyst 100 g, formamide feed 29 g / h, air quantity 2 l / h, surface-specific load 4.8 gl m 2 h.
  • the catalysts used according to the prior art show no approximately constant high selectivity behavior. With the catalysts used according to the invention, however, a consistently high selectivity behavior can be achieved.
  • Example 5 Aluminum oxide chippings from Norton, BET surface area 3.1 m 2 / g, formamide feed 29 g / h, air flow 2 l / h, diluted 1:30 with quartz glass chippings (mixed BET area 0.16 m 2 / g), amount of catalyst 148.5 g, surface specific load 1, 9 gl m 2 h.
  • Example 6 Fe-Al spinel, BET surface area 2 m 2 / g, formamide feed 29 g / h, air volume 2 l / h, 1: 1 1 diluted with quartz glass chippings (mixed BET area 0.19 m 2 / g), grit quantity 156 g, surface-specific load 1, 0 gl m 2 h.
  • Example 7 (comparison): The tests are carried out in a 20 cm long electrically heated empty stainless steel tube (1 .4571). The inner diameter is 3 mm, the reactor inlet pressure 1, 1 bar abs, Formamidzulauf 50 g / h, air 2.1 Nl / h, surface specific load 26540 g / m 2 h.
  • Examples 8 and 9 are carried out in a 20 cm long electrically heated stainless steel tube with silicon coating from Silicotek.
  • the inner diameter is 5.4 mm, the reactor inlet pressure 1, 1 bar abs. and the grit size approx. 2 mm.
  • Quartz chippings BET surface area 0.06 m 2 / g, amount of catalyst 4.6 ml, formamide feed 40 g / h, air quantity 1.7 Nl / h, surface-specific loading 145 g / m 2 h.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'acide cyanhydrique par thermolyse de formamide gazeux dans un réacteur en présence d'un catalyseur, dans lequel a) le catalyseur (i) est un catalyseur à l'oxyde d'aluminium contenant ‑ de 90 à 100 % en poids, de préférence de 99 à 100 % en poids d'oxyde d'aluminium en tant que composant A, ‑ de 0 à 10 % en poids, de préférence de 0 à 1 % en poids de dioxyde de silicium en tant que composant B, et ‑ de 0 à un maximum de 0,1 % en poids de fer ou de composés contenant du fer en tant que composant C, la somme totale des composants A, B et C étant égale à 100 % en poids, (ii) il présente une surface BET, mesurée suivant DIN ISO 9277 : 2003-05, inférieure à 1 m2/g, et (iii) il est recuit à des températures supérieures à 1400 °C pendant 1 à 30 h, de préférence égales ou supérieures à 1500 °C pendant 1 à 30 h et de façon particulièrement préférée à une température de 1500 °C à 1800 °C pendant 2 à 10 h ; et b) la surface interne du réacteur est inerte vis-à-vis de la thermolyse du formamide. L'invention concerne en outre l'utilisation du catalyseur dans un procédé de production d'acide cyanhydrique par thermolyse de formamide gazeux dans un réacteur dont la surface interne est inerte vis-à-vis de la thermolyse du formamide.
EP14718544.1A 2013-04-10 2014-04-09 Procédé de synthèse d'acide cyanhydrique à partir de formamide en présence d'un catalyseur Withdrawn EP2984037A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14718544.1A EP2984037A1 (fr) 2013-04-10 2014-04-09 Procédé de synthèse d'acide cyanhydrique à partir de formamide en présence d'un catalyseur

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13163130 2013-04-10
EP14718544.1A EP2984037A1 (fr) 2013-04-10 2014-04-09 Procédé de synthèse d'acide cyanhydrique à partir de formamide en présence d'un catalyseur
PCT/EP2014/057112 WO2014166975A1 (fr) 2013-04-10 2014-04-09 Procédé de synthèse d'acide cyanhydrique à partir de formamide en présence d'un catalyseur

Publications (1)

Publication Number Publication Date
EP2984037A1 true EP2984037A1 (fr) 2016-02-17

Family

ID=48087437

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14718544.1A Withdrawn EP2984037A1 (fr) 2013-04-10 2014-04-09 Procédé de synthèse d'acide cyanhydrique à partir de formamide en présence d'un catalyseur

Country Status (8)

Country Link
US (1) US20160052793A1 (fr)
EP (1) EP2984037A1 (fr)
JP (1) JP2016519644A (fr)
CN (1) CN105307978A (fr)
BR (1) BR112015025843A2 (fr)
MX (1) MX2015014279A (fr)
RU (1) RU2015148000A (fr)
WO (1) WO2014166975A1 (fr)

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Publication number Priority date Publication date Assignee Title
US1876213A (en) * 1932-09-06 Thohcas ewan
FR668995A (fr) 1928-02-10 1929-11-08 Ici Ltd Procédé et moyens de production de l'acide cyanhydrique
DE3525749A1 (de) 1985-07-19 1987-01-29 Basf Ag Verfahren zur spaltung von formamid zu blausaeure und wasser
DE19962418A1 (de) 1999-12-22 2001-06-28 Basf Ag Kontinuierliches Verfahren zur Herstellung von Blausäure durch Thermolyse von Formamid
DE10132370B4 (de) 2001-07-04 2007-03-08 P21 - Power For The 21St Century Gmbh Vorrichtung und Verfahren zum Verdampfen flüssiger Medien
DE10138553A1 (de) 2001-08-06 2003-05-28 Basf Ag Blausäure aus Formamid
DE10256578A1 (de) * 2002-12-04 2004-06-17 Basf Ag Blausäure aus Formamid
DE10335451A1 (de) 2003-08-02 2005-03-10 Bayer Materialscience Ag Verfahren zur Entfernung von flüchtigen Verbindungen aus Stoffgemischen mittels Mikroverdampfer
DE102005017452B4 (de) 2005-04-15 2008-01-31 INSTITUT FüR MIKROTECHNIK MAINZ GMBH Mikroverdampfer
US8029914B2 (en) * 2005-05-10 2011-10-04 Exxonmobile Research And Engineering Company High performance coated material with improved metal dusting corrosion resistance
ATE529382T1 (de) * 2006-09-07 2011-11-15 Basf Se Verbessertes verfahren zur herstellung von blausäure
AR069295A1 (es) * 2007-11-13 2010-01-13 Basf Se Procedimiento mejorado para preparar cianuro de hidrogeno mediante deshidratacion catalitica de formamida gaseosa
BRPI0820289A2 (pt) * 2007-11-13 2015-05-26 Basf Se Processo para preparar ácido cianídrico, e, uso de um microevaporador.
US9034293B2 (en) * 2008-03-31 2015-05-19 Basf Se Process for preparing hydrocyanic acid by catalytic dehydration of gaseous formamide—direct heating
DE102009012003A1 (de) * 2009-02-26 2010-09-02 Basf Se Schutzbeschichtung für metallische Oberflächen und ihre Herstellung
JP5882229B2 (ja) 2010-01-22 2016-03-09 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ １室型蒸発器及び化学合成におけるその使用

Non-Patent Citations (2)

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Also Published As

Publication number Publication date
JP2016519644A (ja) 2016-07-07
CN105307978A (zh) 2016-02-03
RU2015148000A (ru) 2017-05-15
MX2015014279A (es) 2016-09-28
US20160052793A1 (en) 2016-02-25
WO2014166975A1 (fr) 2014-10-16
BR112015025843A2 (pt) 2017-07-25

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