PL157499B1 - Method of obtaining a mixture of lower aliphatic alcohols from synthesis gases - Google Patents

Abstract

1. The method for producing a mixture of lower aliphatic alcohols from synthesis gas in the presence of a catalyst containing copper, manganese and alkali metal, consisting in that carbon oxide, hydrogen and carbon dioxide making up the synthesis gas are contacted with the catalyst, whose composition is CuxZryMnzAv, where A is alkali metal, x, y, z, v denote molar shares of each metal, where x = 0.377-0.566, y=0.243-0.446, z = 0.204-0.422, v=0.010-0.169, which in terms of metal oxides amounts to 40% by weight, 30-45 CuO, 32-55 ZrO2, 14.5-25 MnO and 0.5-8.0 of alkali metal oxide, the catalyst used in the process having been previously reduced with the synthesis gas under the pressure of 5 MPa at the temperature of 160-280 degrees C, and the process of producing aliphatic alcohols is carried out at the temperature of 250-400 degrees C under the pressure of 10-30 MPa and at the volumetric load of the catalyst with the synthesis gas amounting to 5,000-20,000 h<-1>.

Description

The subject of the invention is a method of producing an alcohol mixture containing one to four carbon atoms per molecule with a predominance of methanol and isoburenol from synthesis gas, containing carbon monoxide, hydrogen and carbon dioxide, in the presence of a copper-cyron-manganese catalyst with the addition of an alkali metal. The ratio follows the following equations

2zH2 + nC0 5 = eCnH ₂ n> 10H ♦ / nl / H ₂ 0/1 / 3nH2 ♦ zC02 ^ SCzH2z + 10H ♦ / 2z-l / H ₂ 0/2 / / n> l / H2 ♦ / 2n-l / C0 3 = 1 ~ _n CzH2 ♦ ^0H / VC0 _2/3 / H20 and CO ♦-ί C0 ₂ ♦ H2 / 4 /

The process of producing a mixture of alcohols from synthesis gas has been known for many years.

In the years 1920 - 1940 in Germany, the methods of obtaining alcohols were patented, mainly with the use of slcalzed iron catalyzers - German patents Nos. 411 216 and 510 302. In the presence of this type of catalyst, a mixture containing alcohol containing from one to nine carbon atoms other compounds was obtained oxygen, water and hydrocarbons, which created a number of technical difficulties related to their separation. Alkalyzed chromium-zinc catalysts were also used, as described in German Patent Nos. 544,565, 565,309 and British Patent Nos. 323,240 to obtain a mixture of alcohols containing from one to six carbon atoms per molecule at a pressure of 29 MPa in g. l: uΓcr 40C ° C. The German Patent Nos. 628 557 and 625 757 describe a process for the production of alkyl alcohols using copper and voliramic alkaline catalysts.

In the Polish patent description No. 107 649 it is stated that at a pressure of 2.0 - 25.0 MPa at a temperature of ¹⁵⁰ - ⁴⁰⁰ ° ^C and the use of an Icatalizator containing copper ^, Icobalt and metal, which may be Cr, Fe, V or Mn and in the presence of alkali mesl, preferably lithium, sodium, polystyrene, are obtained with a yield of more than 100 kg of ethanol per hour of catalyst. According to the Polish Patent Document No. 130 235, a mixture of alcohols from methanol to

157,499 of hexanol was prepared at a temperature of 160-240 ° C under a pressure of 5-15 MPa, using a catalyst containing copper, zinc, aluminum, manganese and alkali metal. On the other hand, in accordance with Polish patent specifications Nos. 135 730 and 145 849, in the process of producing alcohols containing five or more carbon atoms in the molecule, Cu-ZnZn ₃ V · 0g calibrated catalysts were used with the addition of AlgO? or Μη ₂ 0 ₃ · and m kataliz of the catalyst, prepared to 200 kg of a mixture of alcohols.

Summary of the ^ invention is that the carbon monoxide, carbon dioxide, one of hydrogen, included in akła ^dg manhole ^S ntezioe ^g of contacted p. ^A at a temperature ^{of 250} - 400 ⁰ C and ^{P d} pressure 10 - (0 MPa katalrzatoeem with the following composition: Cu * Z ^ Mn2Ay where A - mees! alkaline, x, y, z, v - mole proportions of meeBai: xa 0.377 - 0.566, y 0.243 - 0.446, for 0.204 - 0.422, v> 0.010 - 0.169.

Calculated as oxides of mths constituting the catalyst, the weight percentages are as follows: 30 - 45% by weight of CuO, 32 - 55% by weight of ZrOg, 14.5 - 25% by weight of MnO 1 0.5 - 8% by weight of the oxide an alkali metal, preferably KgO. The catalyst was;) e ^{Si P} o u ^d nio reduction azem ^g s ^{s d} appreciated ntazowym after ^{5 Mp} and at ^^ 1 ^{6 2} 80 ° C.

The use of the method according to the invention makes it possible to obtain a mixture of allietic alcohols with a content of one to four carbon atoms per molecule with high selectivity. The mixture of plβyntizαoa contains only a few percent of water. The reaction proceeds according to equations 1-4, where the water produced in the reaction causes the propagation of CO to CO 2 <in accordance with reaction 4. This allows to increase the amount of alpha alcohols obtained from the catalyst unit of the order of 500 - 1480 kg from 1 m of catalyst per hour. On the other hand, there is practically no hydrocarbons in the exhaust gas.

Example I: Catalyst A. Oo, a pressure reactor with a diameter of 16 mm, equipped with an external electric heating block, was charged with 100 cm of catalyst composed of 30% by weight CuO, 32% by weight ZrOg, 30% by weight MnO and 8% by weight < ₂ 0, which corresponds to the mole fractions of individual metals included in the catalyst: CUo ^ 77 '

Zr0 260 'M ⁿ 0 422 * ^K 0 169 * Then the reactor was purged with nitrogen and the reduction of the catalyst was started with the catalyst gas with the following composition: 5, C% and CO2 volume 22, (% CO volume, 69.5% CO2 volume h ₂ , 1.0 objątościowych CHi% and 2.5% N2 objętoέclowzih "method described below. within 12 hours the synthesis gas flow of 500 Nl / hr. at a pressure of 1.0 MPa, the temperature was raised to ¹⁸ 0 ° C with s ^yb bone ^N rO ^ h ^^ and then NAET ^± 280 ⁰ C with s ^ koścr 10 ° / ^g odzinę. After the envelopment of a temperature of 280 ⁰ C ctontonto raised to ⁵ MPa with 0 srbkością 0.5 Waagodzinę. the reduction of the catalyst was carried out in the parameters achieved for 10 hours. The synthesis of alcoholic alcohols with a molecule containing one to four carbon atoms from carbon monoxide, hydrogen and carbon dioxide was carried out as follows: The reactor was continuously fed with a synthesis gas containing Hg and CO with a molar ratio of 1: 1 and 0.1% by volume of CO % and 20% of nitrogen gas in the reactor the combined thiypeature, process pressure and gas volume load of the catalyst. The reaction gas was directed to the water cooler, then to the separator, where liquid and gas products were separated. The liquid products were subjected to chromytoril analysis. The yield of individual aliphatic alcohols and water obtained in the course of an hour of synthesis is shown in Table 1.

Example II. Catalyst 8. Oo of the reactor analogous to example 3

I was charged with 100 cm of catalyst consisting of 30% by weight of CuO, 55% by weight of ZrO®, 14.5% by weight of MnO and 0.5% by weight of K · O, which corresponds to the mole fraction of metals Cu _Q 377.

Zr0 446 'Mn ^ j:' K 010 * Next, the catalyst was reduced analogously to Example I, and then the catalytic synthesis of alcohols was carried out according to the method given in Example I, using a synthesis gas containing CO and Hg in a molar ratio of CO / Hg = 1 / l and 5% vol. C02 and 10% vol. nitrogen. The process potentials and the yields of individual alcoholic alcohols and water are given in Table 1.

Example III. Catalyst C. Oo of the enatogenic reactor as in example 1 3 was charged with 100 cm of catalyst containing 45% by weight of CuO, 30% by weight of Zr ^, 22% by weight

157 499 by weight ΜπΟ 1 3% by weight K ₂ 0, which corresponds to the molar fraction of individual natall ^Cu 0 566 * ^Zr O 243 * M ' _o 310 * ^Κ 0.064 * The catalyst was reduced in the same way as in example Z, and then the process of alcohol synthesis was carried out, stosujęc Ecy synthesis gas containing CO and H2 in the solo ratio of 1: 1 orez 5% by volume of C0 ₂ and 15% by volume of nitrogen, Paraastry process and the yields of the alcohols shown in table 1,

Example IV. Catalyst O, Oo of the reactor analogous to the example! 100 cm of catalyst containing 30% by weight of CuO, 40% by weight of ZrO ^, 25% by weight of MnO and 5% by weight of K ₂ O were loaded, which corresponds to the proportion of aolovar for individual metals

Cu _Q 377. Zr _Q 328 » ^Mn g ₃₈₂ * K0 106 * NastePnia the catalyst was reduced in the same way as in example 1 and the alcohol synthesis process was carried out using a synthesis gas containing CO and H ₂ in the ratio of eoio« smoke 1: 1 and 10% O ₂ 1 10% by volume nitrogen. The process parameters and the obtained and yields are given in Table 1,

Table 1

Synthesis parameters of alcohols containing 1: 4 carbon atoms per molecule from synthesis gas.

-------- _r --- _γ ---- KaJaJi-. Pressure, temperature, load, embolism, pressure, volume, volume Volume of individual alcohols in kg / m of catalyst per hour

ł 1. ₇ 1 9 Γ ° c w® ₃ 3 • Nm / »^ .h 1 τ ----- methanol 9 1 ethanol vol 9 . . - - J n-propa- ¹ nol 1 - - -. J. isobu- tanol • water 1 u - -. 2 1 r Jalkoholl C1 - c ₄ AND 1 10 1 250 1 5000 , 300 , 50 ¹ 30 ¹ 120 ¹ 180 9 500 1 25 1 320 • 15,000 1 550 '95 i 80 360 1 1 ⁹⁰ 1 1095 . 4 e - «. 4 - - - - - U - - - in . 1.- ·. » B 25 1 350 '10000 '490 '90, 70, 280 1 80 Ł 930 15 320 '15,000 '400 '50 1 60 1 140 160 650 - - - η - - - - «1 r - - C. 22 vol 350 '20,000 '750 and 120 100 ' 450 • 60 1480 thirty 1 400 , 20,000 , 600 , 100 ¹ 60 ' 200 ¹ 100 960 0 22 1 360 1 15,000 1 650 1 ioo ¹ 85 ' 300 '190 1135 thirty 1 300 ¹ 20000 ¹ 480 '90, 90, 150 and 90 810

Department of Publishing of the UP RP. Circulation of 90 copies

Price PLN 5,000.

Claims (2)

Patent Disclaimer 1 · Method for producing alashanl lower aliphatic alcohols from synthesis gas, in the presence of a catalyst containing the same, manganese and alkali metal, so that carbon monoxide, hydrogen and carbon dioxide, which are components of synthesis gas, are in contact with the ketalZzaor with the composition Cu * Zr ^ ^Mn z ^ _v · where a is an alkali metal x, y, z, v, are the mole fractions of individual metals, factor μ · 0.377 - 0.566, yo 0.243 - 0.446, zo 0.204 - 0.422, v »0.010 - 0.169, which in terms of the remaining oxides, respectively 40% by weight, 33-45 CuO, 32-55 ZrO?, 14.5 - 25 MnO and 0.5-8.0 alkali metal oxide, whereby the catalyst used in the process is previously reduced l ^ s gaze teootaym pressurized to 5 MPa, in the TRM ^ 9e turcr ISO ^ - ^ ^{2 Β0} ο for the manufacturing process ol.koholi aUfB ^ ^ble zznych are carried at a temperature of ²⁵⁰ - ⁴⁰⁰ ° C and a pressure of 10-30 EC and a load objątościowya gauze synthesis "of the catalyst of 5000 - 20 ⁰ 00 ^{g _1} cov. A method according to Claim 1, characterized in that the catalyst is low-alkaline potassium. * * »