WO2014166975A1 - Verfahren zur blausäuresynthese aus formamid - katalysator - Google Patents
Verfahren zur blausäuresynthese aus formamid - katalysator Download PDFInfo
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- WO2014166975A1 WO2014166975A1 PCT/EP2014/057112 EP2014057112W WO2014166975A1 WO 2014166975 A1 WO2014166975 A1 WO 2014166975A1 EP 2014057112 W EP2014057112 W EP 2014057112W WO 2014166975 A1 WO2014166975 A1 WO 2014166975A1
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- WIPO (PCT)
- Prior art keywords
- formamide
- thermolysis
- catalyst
- reactor
- gaseous
- Prior art date
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- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 title claims abstract description 181
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims description 51
- 230000002194 synthesizing effect Effects 0.000 title 1
- 238000001149 thermolysis Methods 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 13
- 230000008020 evaporation Effects 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910003465 moissanite Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000002076 thermal analysis method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000007789 gas Substances 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 238000010791 quenching Methods 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- VAYOSLLFUXYJDT-RDTXWAMCSA-N Lysergic acid diethylamide Chemical compound C1=CC(C=2[C@H](N(C)C[C@@H](C=2)C(=O)N(CC)CC)C2)=C3C2=CNC3=C1 VAYOSLLFUXYJDT-RDTXWAMCSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000006189 Andrussov oxidation reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- -1 steel Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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
-
- B01J35/612—
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.
Abstract
Description
Claims
Priority Applications (7)
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CN201480032881.3A CN105307978A (zh) | 2013-04-10 | 2014-04-09 | 由甲酰胺-催化剂合成氢氰酸的方法 |
EP14718544.1A EP2984037A1 (de) | 2013-04-10 | 2014-04-09 | Verfahren zur blausäuresynthese aus formamid - katalysator |
US14/783,314 US20160052793A1 (en) | 2013-04-10 | 2014-04-09 | Method for synthesizing hydrocyanic acid from formamide - catalyst |
MX2015014279A MX2015014279A (es) | 2013-04-10 | 2014-04-09 | Proceso para la síntesis de ácido cianhídrico a partir de catalizador de formamida. |
JP2016506946A JP2016519644A (ja) | 2013-04-10 | 2014-04-09 | ホルムアミド−触媒からのシアン化水素酸の合成法 |
RU2015148000A RU2015148000A (ru) | 2013-04-10 | 2014-04-09 | Способ получения синильной кислоты из формамида на катализаторе |
BR112015025843A BR112015025843A2 (pt) | 2013-04-10 | 2014-04-09 | processo para preparar ácido cianídrico por termólise de formamida gasosa em um reator na presença de um catalisador, e, uso de um catalisador |
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US (1) | US20160052793A1 (de) |
EP (1) | EP2984037A1 (de) |
JP (1) | JP2016519644A (de) |
CN (1) | CN105307978A (de) |
BR (1) | BR112015025843A2 (de) |
MX (1) | MX2015014279A (de) |
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WO (1) | WO2014166975A1 (de) |
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WO2009121827A2 (de) * | 2008-03-31 | 2009-10-08 | Basf Se | Verbessertes verfahren zur herstellung von blausäure durch katalytische dehydratisierung von gasförmigem formamid - direktheizung |
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US1876213A (en) * | 1932-09-06 | Thohcas ewan | ||
DE10256578A1 (de) * | 2002-12-04 | 2004-06-17 | Basf Ag | Blausäure aus Formamid |
US8029914B2 (en) * | 2005-05-10 | 2011-10-04 | Exxonmobile Research And Engineering Company | High performance coated material with improved metal dusting corrosion resistance |
MX2009002357A (es) * | 2006-09-07 | 2009-03-12 | Basf Se | Metodo mejorado para producir acido prusico. |
BRPI0820167A2 (pt) * | 2007-11-13 | 2015-09-29 | Basf Se | processo para preparar ácido cianídrico pela desidratação catalítica de formamida gasosa em um reator tubular, reator, e, uso de um reator |
DE102009012003A1 (de) * | 2009-02-26 | 2010-09-02 | Basf Se | Schutzbeschichtung für metallische Oberflächen und ihre Herstellung |
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2014
- 2014-04-09 RU RU2015148000A patent/RU2015148000A/ru unknown
- 2014-04-09 WO PCT/EP2014/057112 patent/WO2014166975A1/de active Application Filing
- 2014-04-09 CN CN201480032881.3A patent/CN105307978A/zh active Pending
- 2014-04-09 MX MX2015014279A patent/MX2015014279A/es unknown
- 2014-04-09 EP EP14718544.1A patent/EP2984037A1/de not_active Withdrawn
- 2014-04-09 US US14/783,314 patent/US20160052793A1/en not_active Abandoned
- 2014-04-09 JP JP2016506946A patent/JP2016519644A/ja active Pending
- 2014-04-09 BR BR112015025843A patent/BR112015025843A2/pt not_active IP Right Cessation
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DE498733C (de) | 1928-02-10 | 1930-06-02 | Ici Ltd | Verfahren zur Herstellung von Blausaeure |
EP0209039A2 (de) | 1985-07-19 | 1987-01-21 | BASF Aktiengesellschaft | Verfahren zur Spaltung von Formamid zu Blausäure und Wasser |
DE19962418A1 (de) | 1999-12-22 | 2001-06-28 | Basf Ag | Kontinuierliches Verfahren zur Herstellung von Blausäure durch Thermolyse von Formamid |
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MX2015014279A (es) | 2016-09-28 |
JP2016519644A (ja) | 2016-07-07 |
RU2015148000A (ru) | 2017-05-15 |
US20160052793A1 (en) | 2016-02-25 |
CN105307978A (zh) | 2016-02-03 |
BR112015025843A2 (pt) | 2017-07-25 |
EP2984037A1 (de) | 2016-02-17 |
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