UA80099C2 - Catalyst composition for oxidation of ethane and/or of ethylene to acetic acid and method for producing acetic acid - Google Patents

Abstract

A catalyst composition and its use for the selective oxidation of ethane to acetic add and/or for the selective oxidation of ethylene to acetic acid which composition comprises in combination with oxygen the elements molybdenum, vanadium, niobium, gold in the absence of palladium according to the empirical formula: MoaWbAucVdNbeZf wherein Z is one or more elements selected from the group consisting B, Al, Ga, In, Ge, Sn, Pb, Sb, Cu, Pt, Ag, Fe and Re; a, b, c, d, e and f represent the gram atom ratios of the elements such that: 0<a?l;0?b<1 and a+b=l; 10-5 < c ? 0,02; 0<d?2;0<e?1 and 0,0001?f?0,05.

Description

Description of the invention

The present invention relates to a catalyst for selective oxidation of ethane to acetic acid and/or selective 2 oxidation of ethylene to acetic acid, a method of obtaining acetic acid using the aforementioned catalyst.

Catalysts, which include molybdenum, vanadium and niobium in combination with oxygen, intended for use in the processes of obtaining acetic acid by oxidizing ethane and ethylene, are known in this field of technology, for example, from (5 4250346, EP-A-1043064, MO 99/20592 and OE 196 30 8321. 70 In 05 Mo 4250346, the oxidative dehydrogenation of ethane to ethylene in the course of a gas-phase reaction is described with a relatively high degree of conversion, selectivity and productivity at a temperature below approximately 5002 with the use as a catalyst of a composition that includes as elements molybdenum, X and In the ratio

ModXMo, in which X stands for St, Mp, MB, Ta, Ti, M and/or MU, and preferably Mp, MB, M and/or MU; M stands for Vi, Se,

So, Sy, Re, K, Ma, Mi, R, RB, B, 5i, Zp, TI and/or I, and preferably 50, Se and/or y, which means 1, 6 means a number from 0.05 to 1.0, and c means a number from O0 to 2, and preferably from 0.05 to 1.0, provided that the total value of c for Co, Mi and/or Be is less than 0.5.

MO 99/20592 relates to a method for the selective production of acetic acid from ethane, ethylene or their mixtures and oxygen at high temperature in the presence of a catalyst that corresponds to the formula Mo aRaHom, in which X denotes one or more of the following elements: St, Mn, MB, Ta, Ti, M, Te and MU; U means one or more of the following elements: B, At, ba, Ip, RE 7p, Sa, Vi, Se, So, KY, Ig, Sy, Ad9, Ach, Re, Ky, Ov, K, KE, Sv, Ma ,

Ca, 5g, Ba, MB, 2, NE, Mi, R, RB, 5B, 5i, Zp, TI and SHO), and means 1, B means a number from 0.0001 to 001, c means a number from 0.4 to 1, and a means a number from 0.005 to 1.

OE-A1 19630832 refers to a similar catalytic composition, in which a means 1, 5 20, c»0, and a means a number from 0 to 2. In the preferred version, a means 1, B means a number from 0.0001 to 0.5, c means a number from c 0.1 to 1.0, and a means a number from 0 to 1.0. Gee)

The presence of palladium is necessary for the action of catalysts according to both publications MUO 99/20592 and CE 196 30 832.

EP-A 1043064 describes a catalytic composition for the oxidation of ethane to ethylene and/or acetic acid and/or for the oxidation of ethylene to acetic acid; this composition includes in combination with oxygen the elements molybdenum, vanadium, niobium and gold in the absence of palladium according to the empirical formula: b

Fo

MoamBansMam ex (I) (av) wherein M is one or more elements selected from the group consisting of Cg, Mp, Ta, Ti, B, Al, Ca, o

Ip, RI, 2py, Sa, Vi, Se, So, KY, Ig, Si, Ad, Be, Ky, O5, K, KB, Sv, Mao, Sa, 5g, Va, 2t, NE, Mi, R, RB, 56, 5i,

From Zp, TI, O, Ke, Te, I a and Ra; a, B, c, a, is and 7 mean such gram-atomic ratios of elements, in which so 0 "as 1; Osr" 1 ar; 1075 « s « 0.02; O«a«2;O«es 1 and Osiso.

The need to create a catalyst for the oxidation of ethane and/or ethylene to acetic acid and to develop a method of obtaining acetic acid with the use of such a catalyst, in the implementation of which the catalyst creates an opportunity to achieve high selectivity of conversion to acetic acid, remains. -at

It has been found that using a catalyst which, in combination with oxygen, includes the elements molybdenum, vanadium, niobium, and gold, as well as one or more elements selected from the group consisting of boron, aluminum, gallium, indium, germanium, tin, lead, antimony, copper, platinum, silver, iron and rhenium, in the absence of palladium there is a possibility to oxidize ethane and/or ethylene to acetic acid with high selectivity in relation to acetic acid. Moreover, it has been established that the catalysts of this invention can be used to achieve high selectivity for acetic acid with reduced, for example, little, if any, selectivity for ethylene. (a) Accordingly, the present invention provides catalytic composition for the selective oxidation of ethane to acetic acid and/or for the selective oxidation of ethylene to acetic acid, and this composition in combination with oxygen includes the elements molybdenum, vanadium, niobium, gold in the absence of palladium according to (Ce) 50 of the empirical formula: c Moz BAnsMam ek (I) in which 7 means one or more elements selected from the group consisting of B, AT, ba, Ip, Se, 5p, RB, 22 ЗB, Si, Ri, Aa, Re and Ke; a, B, c, d, and i mean such gram-atomic ratios of elements at which

GF) O«a«1;O0s:r«1iYia ri 1; with 1075 « сх 0.02;

O«kasg; in O"es1;i 0.0001 "0.05.

Catalysts covered by formula (I) include:

Mo йAisMamMreZpe

ModAtssMaMieZzpe 65 In the preferred version, 7 means Zp, Ad, Re or Ke, preferably Zp. Examples of acceptable catalysts that correspond to formula (I) include:

Mo» oso Mo 423 MBom15 115 Aitsoyuov Ado ov Ou,

Mo» oso Mo 423 MBom15 Amosov Geo, ой5в Оу,

Mo» oso Mo 423 MBom15 AMooov Keo osv Oh,

Mo» oso Mo 423 MBom15 AMooov ZPo obov OU Y

Mo oso Mod2z MbBo,117 AMoyov ZPooi56 Оу, where у means the number that corresponds to the valences of the elements in the composition for oxygen.

Preferably 0.01 « a « 1. In the preferred version 0.1 « a « 2. Preferably 0.01 « e « 0.5, for example, 005 «ke s 0.15. In the preferred version, 0.0005 « 1 « 0.02. 70 The advantage of the catalytic compositions according to the present invention is that they are highly selective in converting ethane and/or ethylene into acetic acid. Using the catalytic compositions of the present invention, a selectivity to acetic acid of typically at least 50 moles to, preferably at least 60 moles of 95, particularly at least 70 moles of 905 can be achieved.

Thus, in particular, using the catalytic compositions according to the present invention, high selectivity with respect to 75% acetic acid can be achieved in combination with low, if any, selectivity with respect to ethylene.

When using the catalytic compositions according to the present invention, the selectivity with respect to ethylene is usually less than 25 mol 9o, preferably less than 10 mol 9o, in particular less than 5 mol 9.

In a preferred embodiment, when using the catalytic compositions according to the present invention, the selectivity with respect to acetic acid is at least 95 mol, in particular at least 70 mol 905, and the selectivity with respect to ethylene is less than 15 mol 90, in particular less than 10 mol 9.

As used herein, the term "selectivity" refers to the percentage that represents the amount of target acetic acid that is obtained as a product compared to the total amount of carbon in the products that are formed: Ha selectivity, 95 - 100 7 the number of moles of acetic acid obtained/5 where 5 means the sum of the molar equivalents of acid (on a carbon basis) of all carbon-containing products, with the exception of alkanes, in the waste stream.

These catalytic compositions can be prepared by any of the methods that are usually used in the preparation of catalysts. Such a catalyst can be successfully prepared from a solution of soluble compounds or d) complexes and/or compounds of each of the metals. In the preferred version, the solution is an aqueous system, the pH value of which is in the range from 1 to 12, preferably from 2 to 8, at a temperature from 20 to 10096. o

Usually, a mixture of compounds containing such elements is prepared by dissolving sufficient amounts of soluble compounds and dispersing all insoluble compounds in order to achieve the target gram-to-atom ratio of elements in the catalytic composition. Further, the catalytic composition can be prepared by removing the solvent from the mixture. The catalyst can be calcined by holding at a temperature of 200 to (C) 5502 C, preferably in air or in oxygen, for a period of 15 to 24 hours. Preferably, the air or oxygen is a slowly moving stream.

The catalyst can be used unsupported or supported. Acceptable carriers include silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, silicon carbide, and mixtures of two or more carriers. - c Additional details of the acceptable method of preparation of the catalytic composition can be found, for example, in (ЕР-А а 0166438). ,» The catalyst can be used in the form of a fixed or fluidized bed.

In another variant, the present invention provides a method for the selective production of acetic acid from a gaseous mixture that includes ethane and/or ethylene, and this method includes introducing the gaseous mixture into (ee) contact with a gas that contains molecular oxygen at an elevated temperature in the presence of a catalytic about the composition presented above in this description.

Ethane is selectively oxidized to acetic acid and/or ethylene is selectively oxidized to acetic acid. In (a) a preferred embodiment, ethane and optionally ethylene are oxidized to a mixture that includes acetic acid, which can be used with or without the addition or removal of acetic acid to produce vinyl acetate by reaction with a gas containing molecular oxygen in a joint process. (Che) The feed gas includes ethane and/or ethylene, preferably ethane.

Ethane and/or ethylene may be used in substantially pure form or mixed with one or more of such substances as nitrogen, methane, carbon dioxide and water in the form of water vapor, which may be present in significant amounts, for example greater than 506.96, or with one or by several substances such as hydrogen, carbon monoxide, C3/C; alkenes and alkenes which may be present in small quantities, for example less than 506.90.

The gas containing molecular oxygen can be air or a gas richer or poorer in molecular oxygen than air, such as oxygen. An acceptable gas may be, for example, oxygen diluted with a suitable diluent, such as nitrogen. 60 In a preferred embodiment, in addition to ethane and/or ethylene and a gas containing molecular oxygen, water (water vapor) is introduced, as this can improve the selectivity to acetic acid.

A suitable elevated temperature can be in the range from 200 to 5002, preferably from 200 to 40026.

The target pressure can be atmospheric or elevated, for example in the range from 1 to 50 bar, preferably from 1 to 30 bar.

In a preferred embodiment, before use in the method according to the invention, the catalytic composition is calcined.

Acceptable calcination can be carried out by holding at an elevated temperature, preferably in the range from 250 to 5002C, in the presence of an oxygen-containing gas, such as air.

Working conditions and other information that can be used for the implementation of the invention can be obtained from the above-mentioned literature dedicated to this field of technology, for example, from OZ Mo 4250346.

The method according to the invention is further illustrated with reference to the following examples.

Preparation of catalyst

Preparation of catalyst A (comparative)

Solution "A" was prepared by mixing 22.935 g of ammonium molybdate and 0.0357 g of ammonium tetrachloroaurate in 100 ml of 7/0 distilled water at 702C. Solution "B" was prepared by mixing 6.434 g of ammonium vanadate in 150 ml of distilled water at 702C. solution "B" was prepared by mixing 7.785 g of niobium ammonium oxalate in 100 ml of distilled water at 702C. Each of the solutions A, B and B was left to stand for 15 minutes in order to provide an opportunity for maximum solubilization of the components. Then, with stirring at 702, solution B was quickly introduced into solution B The mixed solution B/B was stirred for 15 min at 702C, 715 was then rapidly introduced into the solution. the mixture of reagents was stirred for 1.5 hours, as a result of which a dry paste was formed. Then the chemical beaker with the dried paste was transferred to a drying cabinet for additional drying at 120 C for 2 hours. After drying, the catalytic precursor was ground to a fine powder, and then sieved through a sieve with a cell size of 0.2 mm. Next, the cake obtained from the powdered catalyst was calcined in still air in a drying cabinet at 4002 for 4 hours. The prepared oxide catalyst corresponded to the following nominal formula:

Mo» oso Mo 423 MBo, 115 AMo ooov Ou sch

This catalyst was not a catalyst according to the invention because it did not contain an element of the group 75 that includes B, A, Ca, Ip, Se, Zp, RB, 55, Si, Ri, Aod, Re and Be. at

Preparation of catalyst B

Catalyst B was prepared in the same way as catalyst A, except that 0.0190 g of stannous chloride (II) was additionally added to solution A. The prepared oxide catalyst corresponded to the following nominal formula: F zo Mo» oso Mo 423 MBo 115 АMo

Preparation of the catalyst in Ge")

Catalyst B was prepared in the same way as catalyst A, except that 0.3792 g of tin(I) chloride was added to solution A. The prepared oxide catalyst corresponded to the following nominal formula: o

Mo» oso Mo 423 MBo, 117 AMo ov ZPo 0156 Ou (av)

Preparation of catalyst G 35 Catalyst G was prepared in the same way as catalyst A, but with the addition of 0.0299 g of antimony (P) acetate (EMU 298.88) to solution A. Thus, the oxide catalyst corresponded to the following nominal formula:

Mo" oso Mo 423 IMBo, 115 AMo sov ZBo ov Ou

Preparation of catalyst D "

Catalyst D was prepared in the same way as catalyst A, but with the addition of 0.0200 g of copper(P) acetate C t0 (EMU 199.65) to solution A. Thus, the oxide catalyst corresponded to the following nominal formula: с Мо осо Мо2з Мбо 1415 АМцо сов СМ оов Оу "» Preparation of catalyst E ". .

Catalyst E was prepared in the same way as catalyst A, but with the addition of 0.0027 g of platinum acetate (EMU 352.66) to solution A. Thus, the oxide catalyst corresponded to the following nominal formula: 45 so Mo oso Mo 423 Mbo 115 AMco sov РЮ особ Оу

Preparation of catalyst E "in Catalyst E was prepared in the same way as catalyst A, but with the addition of 0.0174 g of silver(I) acetate (RMU 166.92) to solution A. Thus, the oxide catalyst corresponded to the following nominal formula: и Мо осо Мо 423 Мбо 115 Ацо сов АЧо сов Оу (се) Preparation of catalyst Ж с Catalyst Ж was prepared in the same way as catalyst A, but with the addition of 0.8080 g of iron nitrate to solution A (W) (EMU 404.00). Thus, the oxide catalyst corresponded to the following nominal formula:

Mo» oso Mo 42z MBO, 115 AMooov Reoo156 Ou

Preparation of catalyst Z

Catalyst C was prepared in the same way as catalyst A, but with the addition of 0.0268 g of ammonium rhenate (EM

GF) 268.24). Thus, the oxide catalyst corresponded to the following nominal formula:

Preparation of the catalyst J

Catalyst I was prepared in the same way as catalyst A, but with the addition of 0.0256 g of gallium nitrate (EM/ 60 255.74) to solution A. Thus, the oxide catalyst corresponded to the following nominal formula:

Mo» oso Mo 42z IMBo, 115 AMo, sov av oov Ou

The general method of carrying out the ethane oxidation reaction

As a rule, 5 ml of powdered catalyst from A to I was mixed with 15 ml of glass beads with a diameter of 04 mm, obtaining a layer of diluted catalyst with a volume of 20 ml. Then this diluted catalyst was loaded into a reactor with a fixed bed made of Hastelloy alloy, with an internal diameter of 12 mm and a length of 40 cm. The catalyst was held in the center of the reactor by quartz wall pins along with an inert packing material above and below the catalyst layer. Next, to check for leaks, the reactor was tested under a helium pressure of 20 bar. After that, in helium under a pressure of 16 bar, the catalyst was activated by heating to 220 2C at a rate of 59 Cb/min and holding for 1 hour in order to guarantee complete decomposition of the catalytic precursors.

Then, streams of ethane, ethylene, 2095 oxygen in helium and water, necessary to guarantee the creation of the desired input composition, were introduced into the reactor. This composition included 5206.95 ethane, 6,706.95 oxygen, 1006.95 ethylene, 506.95 water, and the rest - helium. The total consumption of raw materials was maintained at such a level, at which 70 SSHPG from 2000 to 9000/hour was guaranteed. After establishing equilibrium within 60 min, gas samples were taken from the waste stream for the GC system (pisat model 4400) for the purpose of quantitative determination of ethane, ethylene, oxygen, and helium.

In order to facilitate a direct comparison, in order to achieve in the reactor for each of the catalysts from A to IY a similar temperature from 299 to 301 °C, the temperature in the reactor, which is set, was increased to 29390. After the end of another period of establishing equilibrium for two minutes, the liquid product was collected and this 75 process was continued for usually 18 hours. During the experimental period, the composition of the waste gas was determined by GC analysis (RgossS, Opisat). The volume of waste gas over the entire period of the experiment was measured with a water/gas flow meter. After the experimental period, liquid products were collected and weighed. The composition of liquid products was determined by gas chromatographic analysis (Opisat devices, models 4400 and 4200, equipped, respectively, with a thermal conductometric detector (TCD) and a flame ionization detector (FID).

Based on the analysis of the flow rates and the composition of the starting materials and products, the following parameters were calculated: the degree of ethane conversion: (number of moles of ethane at the inlet - number of moles of ethane at the outlet)/number of moles of ethane at the inlet x 100 oxygen: (number of moles of oxygen at the inlet - number moles of oxygen at the outlet)/number of moles of oxygen at the inlet x 100 Ha selectivity in relation to acetic acid (C, moles 905): (number of moles of acetic acid x 2 at the outlet) (number of moles of ethylene x 2 at the outlet - number of moles of ethylene x 2 at the inlet) and the number of moles of CO at the outlet - the number of moles of COo at the outlet and the number of moles of acetic acid x 2 at the outlet) x 100 He") in the ratio of ethylene (C, mole 905): (number of moles of ethylene x 2 at the outlet ( (number of moles of ethylene x 2 at the outlet - number of moles of ethylene x 2 at the inlet) - number of moles of CO at the outlet - number of moles of CO" at the outlet i- number o of moles of acetic acid x 2 at the outlet) x 100 o in the ratio of CO (С , molar 95): (number of moles of CO at the outlet)((number of moles of ethylene x 2 at the outlet - number of moles of ethylene x 2 n and inputs) - the number of moles of CO at the outlet i - the number of moles of CO" at the outlet i - the number of moles of acetic acid

ACIDS X 2 at the outlet) x 100 ee in the ratio of CO" (C, molar 95): (number of moles of CO" at the outlet (number of moles of ethylene x 2 at the outlet - number of moles of ethylene x 2 at the inlet) - number of moles of CO at the outlet i- the number of moles of CO" at the outlet i- the number of moles of acetic acid x 2 at the outlet) x 100 " in relation to CO: selectivity in relation to CO (C, 90 moles) i- selectivity in relation to CO" (C,

Molnykh 95) OPR (volumetric productivity), 90: (g of acetic acid)/kg of catalytic layer/h. - c As a rule, the mass balance and carbon balance for the reaction was equal to, as it was established, 100-- 595. a Experiment A and examples from 1 to 9 "» In the implementation of the above-described general method of conducting the reaction, each of the catalysts from A to K was used. The results are presented in Table 1. Each catalyst was evaluated under the usual 475 conditions listed in Table 1. (ee) Conditions: o 520o6.95 ethane, 6,706.95 oxygen, 100o6.95 ethylene, 5 vol.95 water, the rest - helium.SSHPG: 3200 h ", 16 bar.

The results presented in Table 1 clearly indicate that when compared with the comparative (c) catalyst, catalyst A, the catalysts according to the present invention ensure the achievement of a higher c 50 selectivity in relation to acetic acid. Moreover, high selectivity in relation to acetic acid is achieved in combination with reduced selectivity in relation to ethylene. iChe)

IY ethane, C, C, minor. minor AsonNg/kg mol. СсОо,,с, cat./h

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Claims (12)

The formula of the invention 1. Catalytic composition for the selective oxidation of ethane to acetic acid and/or for the selective oxidation of ethylene to acetic acid, which in combination with oxygen contains the elements molybdenum, vanadium, niobium, gold in the absence of palladium according to the empirical formula: 70 wherein 7 represents one or more elements selected from the group consisting of B, AI, (za, Ip, se, 5p, RB, ZV, Sy, RI, Ho, Re and Ke; a, B, c, d, е and и mean such gram-atomic ratios of elements in which О«ае1; О«р«1 and анр-1; 105«с« 0.02; Oka«2Oskest and 0.0001-1с0.05. 2. The catalytic composition of the 1, уакийОО1й «а«1,01»а:2,0,01 «ke «0,51 0,0005 «и» 0,02. 3. Catalytic composition according to one of the previous items, in which 7 means Zp, Ao9, Re or Ke. 4. Catalytic composition according to item C, in which 7 means 5p. 5. Catalytic composition according to claim 4, in which the formula I is selected from the group that includes Mo AUMiatsoMaMBezpe and MozAisMamMrezp. 6. Catalytic composition according to claim 1, which corresponds to the formula selected from the group that includes Mo» osoMo 423 MBo 115 Mo 0ovAdo oovOu; Mo» oooMo 42zIMBo 1150 sov Geo o156Ou; Mo» osoMo 423MBo 115 Mo ov Keo osv Ou, s Mo» ooMo 42zIMBo 115lM0 0008 Z Po, ooov Ou and o Mo osoMo 423YMBo 117AMo obov ZPooiii56Ou, where y means the number that corresponds to the valences of the elements in the composition for oxygen. 7. A method of obtaining acetic acid from a gaseous mixture that includes ethane and/or ethylene, which includes introducing the gaseous mixture into contact with a gas that contains molecular oxygen at an elevated temperature. In the presence of a catalytic composition according to one of the previous items. 8. The method according to claim 7, in which ethane and optionally ethylene are oxidized to a mixture that includes acetic acid. Me. 9. The method according to claim 7 or 8, in which the elevated temperature is in the range from 200 to 50090. o 10. The method according to one of claims 7-9, in which the pressure is in the range from 1 to 50 bar. 11. The method according to one of claims 7-10, in which the selectivity of the oxidation reaction of ethane and/or ethylene to acetic acid is at least 50 mol.bo. Ev 12. The method according to claim 11, in which the selectivity of the oxidation reaction of ethane and/or ethylene to acetic acid is at least 60 mol.oo. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated "microcircuits", 2007, M 13, 27.08.2007. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. . and? (ee) («c) («c) se) iChe) ime) 60 b5