Method of preparing catalyst for oxidation and ammoxidation of olefins

FIELD: chemistry.

SUBSTANCE: mixed metal oxide catalyst based on antimonite in a catalytic active oxidation state has the empirical formula: MeaSbbXcQdReOf, where Me is at least one element from the group: Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th, Ce, Pr, Sm, or Nd; X is at least one element from the group: V, Mo, or W; Q is at least one element from the group: Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Zr, Hf, Nb, Ta, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Pb, As, or Se; R is at least one element from the group: Bi, B, P, or Te; and the indices a, b, c, d, e and f denote atomic ratios: a has a value from 0.1 to 15; b has a value from 1 to 100; c has a value from 0 to 20; d has a value from 0 to 20; e has a value from 0 to 10 and f is a number, taken to fulfill the valency requirements of the metals answering for the oxidation degree they have in the composition of the catalyst. Method of obtaining such a catalyst includes the following stages. At first they are subjected to aqueous suspension of Sb2O3 with HNO3 and with one or more compounds of Me, and voluntarily with one or more compounds from the groups: X, Q or R, for obtaining the first mixture (a). The first mixture is then heated and dried to form a solid product (b). After this the solid product is calcinated forming the catalyst. The particular metal oxide catalyst based on antimonite in the catalytic active oxidation state as per the invention has the empirical formula: Ua'FeaSbbMocBieOf, where the indices a, a', b, c, e and f denote atomic ratios: a has a value from 0.1 to 5; a' has a value from 0.1 to 5; b has a value from 1 to 10; c has a value from 0.001 to 0.2; e has a value from 0.001 to 0.2; and f is a number, taken to fulfill the valency requirements of Sb, U, Fe, Bi, and Mo, answering for the oxidation degree they have in the composition of the catalyst. Method of obtaining such a catalyst includes the following stages. At first they are subjected to aqueous suspension of Sb2O3 with HNO3, oxides or nitrates of bismuth and oxides or nitrates of uranium to form the first mixture (a). The first mixture is then heated under temperature and in a period of time, enough for the induction of the process for the formation of the antimonic oxide crystals and formation of the second mixture (b). An aqueous solution of a ferric compound iss then added to the second mixture for the formation of a third mixture (c). The pH of the third mixture is regulated in the range of 7 - 8.5, a precipitate of a hydrated mixture of oxides in the aqueous phase is formed (d). The precipitate is separated from the aqueous phase (e). An aqueous suspension of precipitate components of hydrated mixed oxides is obtained (f). Molybdate is added to the suspension component of hydrated mixed oxides (g). A suspension of hydrated mixed oxides of Molybdate component in the form of dy particles is formed (h). Later the calcination of the dry particles with the formation of the catalyst is carried out (i).

EFFECT: increase in the activity and selectivity of the catalyst.

30 cl, 2 tbl, 7 ex

 

BACKGROUND of the INVENTION

This invention relates to a method for producing mixed metal oxide catalysts on the basis of antimonate and made of these catalysts. Further, this invention relates to the use of mixed metal oxide catalysts on the basis of antimonate described in this invention, the reactions ammoxidation or oxidation of organic compounds.

It is known that contains antimony metal-oxide catalysts, especially those containing oxides of antimony and at least one metal from the group iron, cobalt, Nickel, tin, uranium, chromium, copper, manganese, titanium and cerium, suitable for the production of aldehydes and carboxylic acids by oxidation of organic compounds, i.e. olefins; to get dienes, unsaturated aldehydes and unsaturated acids by oxidative dehydrogenization olefins, as well as to obtain NITRILES by ammoxidation olefins, alcohols and aldehydes.

There are various catalytic methods for oxidation or ammoxidation olefins. Typically, these processes involve the interaction in the vapor phase olefin or mixture of olefins and ammonia with oxygen in the presence of a catalyst. To obtain acrolein and Acrylonitrile as the olefin reactant used primarily propylene, and to obtain methacrolein and Methacrylonitrile is as olefinic reactant is mainly used isobutene.

Described a large number of catalysts suitable for the oxidation and/or ammoxidation olefins, including catalysts described in U.S. patent No. 5094990; 4590175; 4547484; 4487850 and 4413155. One such catalysts are described in U.S. Patent No. 4547484. This catalyst has the empirical formula:

SbaUbFecBidMocOf

where a has a value from 1 to 10; b has a value from 0.1 to 5; C has a value from 0.1 to 5; d has a value from 0.001 to 0.1; e has a value from 0.001 to 0.2; and f is a number taken to satisfy the valence requirements of the elements Sb, U, Fe, Bi and Mo, corresponding to the degree of oxidation, which they have in the composition of the catalyst. The methods of preparation of these catalysts include adding to the reactor a solid, mostly crushed, antimony, adding antimony in the form of metal or in the form Sb2O3.

Although the yield and selectivity of the above catalysts in General satisfactory, the use of catalytic systems for commercial purposes to a large extent depends on its value from the conversion reagent (reagents), from the output of the target product (target product) and the stability of the catalyst during the reaction. In many cases, the cost reduction catalytic system for a few cents per pound, or a slight percentage increase in output Clevo what about the product of great economic importance. It is known that the economy of manufacture of Acrylonitrile requires increasing the outputs of the process and high selectivity of conversion of the reactants in the Acrylonitrile, therefore, to reduce the difficulties associated with the purification of the target product and the treatment of recirculating flow of a large volume, are conducted systematic research to seek new or improved catalytic systems, to develop methods and ways of cooking old and new catalytic systems that reduce the cost of the target product and/or improved activity and selectivity.

It is desirable to create a catalyst that improves the reproducibility and homogeneity, which contains significantly less αSb2O4and if it provides an equivalent or higher degree of catalytic transformations. So we believe that the discovery of improved catalysts and the method of their preparation, are described in this invention, will contribute significantly to the progress in this field.

SUMMARY of INVENTION

According to this invention describes a method of preparation of the mixed metal oxide catalyst based antimonate in a catalytically active oxidized state; the catalyst has the empirical formula:

MeaSbbXcQdReOf

<> where Me is at least one element from the group of Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th, Ce, Pr, Sm or Nd; X is at least one element from the group of V, Mo or W; Q is at least one element from the group of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Zr, Hf, Nb, TA, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Pb, As, or Se; R is at least one element from the group of Bi, b, P or Te; and the indices a, b, C, d, e, and f represent atomic relations: a has a value from 0.1 to 15; b has a value from 1 to 100; C is from 0 to 20; d is from 0 to 20; e has a value from 0 to 10; and f is a number taken to satisfy the valence requirements of the metals corresponding to the degree of oxidation, which they have in the composition of the catalyst; the method includes:

(a) the contact of the aqueous suspension Sb2O3from HNO3and with one or more compounds Me and arbitrarily with one or more compounds from the group: X, Q or R to obtain a first mixture;

(b) heating and drying the first mixture, resulting in a solid product; and

(c) calcining the solid product to form the catalyst.

Further, according to this invention describes a mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, prepared according to the method of the present invention.

In addition, according to this invention describes methods of ammoxidation, oxidation and hydroxy is gidrogenizatsii using mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, prepared according to the method of implementation of this invention.

BRIEF DESCRIPTION of DRAWINGS

Is missing.

DETAILED DESCRIPTION

The catalysts which can be prepared according to the process of this invention include, without limitation, those catalysts which have the empirical formula given in U.S. patent No. 5094990; 4590175; 4547484; 4487850 and 4413155, the contents of which are incorporated herein by reference.

This invention describes a method of preparation of the mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, the catalyst has the empirical formula:

MeaSbbXcQdReOf

where Me is at least one element from the group of Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th, Ce, Pr, Sm or Nd; X is at least one element from the group of V, Mo or W; Q is at least one element from the group of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Zr, Hf, Nb, TA, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Pb, As, or Se; R is at least one element from the group of Bi, b, P or Te; and the indices a, b, C, d, e, and f represent atomic relations:

a has a value from 0.1 to 15, preferably from 0.1 to 10, more preferably from 0.1 to 5;

b has a value from 1 to 100, preferably from 1 to 50, more preferably from 1 to 10;

C has values from 0 to 20, preferably from 0.001 to 5, more preferably from 0.01 to 10;

d has a value from 0 to 20, preferably from 0 to 10;

e has a value from 0 to 10, preferably from 0.01 to 5; and

f is a number taken to satisfy the valence requirements of the metals corresponding to the degree of oxidation, which they have in the catalyst composition.

Particularly preferred catalyst described in this invention has the empirical formula:

Ua′FeaSbbMocBieOf

where a and a′ independently selected in the range from 0.1 to 5, preferably from 0.1 to 1; b has a value from 1 to 10, preferably from 1 to 5; C has a value from 0.001 to 0.2, preferably from 0.01 to 0.1; and e has a value from 0.001 to 0.2, preferably from 0.01 to 0.05.

The catalyst described in this invention to prepare an improved method, which includes:

(a) the contact of the aqueous suspension Sb2O3from HNO3and with one or more compounds Me, preferably with compounds monoxide Me or nitrate Me, and arbitrarily with one or more compounds from the group: X, Q or R to obtain a first mixture;

(b) heating and drying the first mixture, resulting in a solid product; and

(c) calcining the solid product to form the catalyst.

Preferred elements selected Me of: Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th or CE, which is currently the most predpochtitel the YMI are Fe and U. Preferred R elements selected from Bi, Te or R, of which currently, the most preferred is Bi. Currently, the most preferred element X is Mo. The preferred elements of Q selected from Mg, Ca, Zr, Nb, TA, Zn, Al, Ga, and Pb. If the catalyst contains more than one member of a specific group, i.e. more than one element Me, then the index of each element of specific groups independently selected according to the definition of this particular index. For example, if Me selected in such a way that includes U and Fe, each index "a" is independently selected in the range from 0.1 to 15, preferably from 0.1 to 10, more preferably from 0.1 to 5.

Compounds containing Me and is suitable for use in the method of this invention include the oxides and nitrates. Examples of suitable compounds Me without restrictions include oxide-oxide of uranium, uranium dioxide, uranium nitrate and ferric nitrate. If Me is iron (III), compounds of Fe may also include Fe2(SO4)3, Fe(OH)3and FeCl3. If Me is iron (III), the preferred connection Fe is iron nitrate.

Suitable for the method of the present invention compounds containing elements X, Q, and R, include compounds capable of dissolution in acidic conditions, such as oxides, nitrates, chlorides and sulfatide same products of their transformation. The preferred compounds are the oxides and nitrates. For example, compounds containing elements X, Q, and R, can be added in the form of oxides or nitrates, in the form of corresponding salts, or can be arbitrarily added in the form of oxides or nitrates, reacting in situ with the formation of the corresponding salts. Examples of suitable compounds X include molybdenum oxide, tungsten oxide, vanadium oxide, ferric molybdate, ammonium molybdate, metabolomic ammonium and ammonium metavanadate. Examples of suitable compounds R include trioxide bismuth nitrate bismuth, tellurium dioxide, phosphoric acid, ammonium salts of phosphoric acid, pathiakis phosphorus and boric acid. Examples of suitable compounds Q include potassium nitrate, magnesium oxide, magnesium nitrate, zirconium oxide, aluminum oxide, aluminum nitrate, zinc oxide and zinc nitrate.

The method of this invention provides that the suspension Sb2O3was in contact with HNO3. In the method of the present invention HNO3can be added to the aqueous slurry Sb2About3or, on the contrary, the aqueous suspension Sb2O3can be added to HNO3. Currently preferred is the addition of HNO3to the aqueous slurry Sb2O3. Water suspension Sb2About3can be prepared and used in the directly in the preparation process described in this invention catalyst or water suspension Sb 2About3can be prepared and stockpiled for later use in the preparation described in this invention catalyst. Water suspension Sb2About3can be prepared according to any method known in this field. You can also use commercially available suspension Sb2About3such as is commercially available colloidal Sb2About3that can be very effective in the process described in this invention. At present prefer to contact water suspension Sb2About3from HNO3the suspension was prepared under conditions of a high degree of dispersion or mixed in a high degree of dispersion. The use of aqueous suspensions Sb2About3in the implementation method of this invention results in a catalyst with improved homogeneity and with significantly less content αSb2About4in the target catalyst, such a catalyst provides an equivalent or higher degree of catalytic conversion than the catalyst prepared using powdered oxide of antimony.

Before heating and drying stage (b), before the addition of compounds of the element X of the first mixture is preferably heated to convert the original αSb2 About4in other crystalline oxides of antimony, including βSb2About3i.e. at least part of antimony trioxide translate into higher levels of oxidation, for example, is turned into cityregional and patikis antimony. Particularly preferable to use this stage of heating in the case when the first mixture is added to an oxide of uranium. The time required for the formation of the desired crystalline form of the oxide of antimony, may vary and depends, at least in part, on the applied temperature. Usually a sufficient time interval within about 1-6 hours, preferably about 2-5 hours at a temperature of about 80-110°C.

The catalyst described in this invention can be applied in the presence of the carrier, or without it. In some applications prefer to include in the catalyst material of the carrier, which provides more reactive catalytic surface, forming a more solid and durable catalyst for use in highly abrasive environment of the reactor with a fluidized bed of catalyst. The material of the carrier may be any of the commonly proposed for such use of the substance, such as quartz, zirconium dioxide, alumina, alumina, titanium dioxide, colloidal solution of antimony pentoxide or other is kinim substrate. From the point of view of availability, cost and operation of the quartz is usually satisfactory material as the carrier and is preferably in the form of easily dispersible Zola silica.

Ratios involving components of the catalyst on an inert carrier, can vary within wide limits, but generally prefer the content of the media about 10-90 weight percent, and more preferably about 35-65 weight percent, of the total combined weight of catalyst and carrier. To enable the carrier in the catalyst material of the carrier, along with the first mixture is preferably suspended in water, preferably after the step of heating to form a crystalline oxide of antimony with appropriate pH value and while maintaining the fluidity of the suspension. When the material of the carrier is basic, the pH may be approximately 7-9. When the material of the medium is acidic, type acidic Sol of silica, it is desirable suspensions with low pH value (pH<4). Preparation of suspension will depend on the specific material used media, and these conditions of preparation will be obvious for a skilled specialist.

If necessary the pH of the first mixture to regulate the heating and drying step (b). Depending on the specific catalyst is, the possible need for uregulirovania pH by its increase or decrease.

From the thoroughly mixed suspension by heating remove most of the aqueous phase. Concentrated suspension contains a certain amount of water, and it is desirable to remove this water by some means of drying in order to obtain the dry catalyst precursor. Such a method of drying can be as simple as drying Cabinet, in which water-containing solid phase is subjected to processing temperature high enough to evaporate the water and completely dry the solid phase.

An alternative method of drying, which can be used is the so-called spray drying. This method, which is preferred for the present invention, involves the spraying particles of a solid phase containing water, a camera with a hot gas (usually air) to the evaporation of water. This drying process is governed by the temperature of the gas and the length of the path of movement of the particles in the gas environment. In General, it is desirable to adjust these parameters in order to avoid too rapid drying, as this can lead to the formation of a leathery cover partially dried particles of the solid phase, which subsequently is broken because the water contained within the particles evaporates and tends to evaporate. In the about the same time it is desirable to give the catalyst in this form, so he swallowed possibly less water. So, if you are using a reactor with a fluidized bed of catalyst and want to get microspherical particles, it is desirable to select conditions for spray drying in order to achieve substantially complete drying without destroying the particles.

After drying the catalyst precursor calicivirus order to obtain an active catalyst. Typically, the calcination is conducted in air at the required atmospheric pressure and a temperature of approximately 500-1150°C, preferably at 600-900°C. the Time required for complete calcination may vary and will depend on the applied temperature. In General, the duration of the calcination can be up to 24 hours, but for most purposes a sufficient period of time approximately 1-4 hours at the same temperature.

The preferred method of preparation of the catalyst described in this invention, following the example of the preferred in the present catalyst described in this invention, which has the following empirical formula:

Ua′FeaSbbMocBieOf

where a and a′ independently selected in the range from 0.1 to 5, b has a value from 1 to 10, p has a value from 0.001 to 0.2, and e has a signature is to be placed from 0.001 to 0.2. Although the preferred method described in the preferred example in the present catalyst of the present invention, however, this preferred method can be used with love by the catalyst of this invention by appropriate selection of reactants and the specific reaction conditions.

In the preferred embodiment of this invention describes the method of preparation of the mixed metal oxide catalyst based antimonate in a catalytically active oxidized state; the specified catalyst has the following empirical formula:

Ua′FeaSbbMocBieOf

where the indices a, and′a, b, C, e, and f represent atomic relations; and has a value from 0.1 to 5; and′ has a value from 0.1 to 5; b has a value from 1 to 10; C has a value from 0.001 to 0.2; e has a value from 0.001 to 0.2; and f is a number taken to satisfy the valence requirements of Sb, U, Fe, Bi and Mo, corresponding to the degree of oxidation, which they have in the composition of the catalyst; the method comprises:

(a) the contact of the aqueous suspension Sb2About3from HNO3and oxides or nitrates of bismuth and oxides or nitrates of uranium to obtain a first mixture;

(b) heating the first mixture at a temperature and for a time sufficient to induce formation of the desired cristalli the definition of oxides of antimony (including β -Sb2About3and other oxides of antimony, for example at least part of antimony trioxide, which is transformed into a form with a higher degree of oxidation, for example in cityregional antimony and patikis antimony) and the formation of the second mixture;

(c) adding an aqueous solution of compounds of trivalent iron to the second mixture for formation of the third mixture;

(d) adjusting the pH of the third mixture within about 7-8 .5 and the formation of a precipitate of hydrated mixed oxide in the aqueous phase;

(e) separating the precipitate of hydrated mixed oxide from the aqueous phase;

(f) formation of aqueous suspension of the sedimentary component of hydrated mixed oxide;

(g) the addition of molybdate to the suspension component of hydrated mixed oxide;

(h) formation of a suspension of hydrated mixed oxide-molybdates component in the form of dry particles; and

(i) calcining the dry particles for the formation of the catalyst.

During the formation of the first mixture at the present time prefer to contact water suspension Sb2About3with oxides or nitrates of bismuth and uranium to make contact HNO3with a water suspension Sb2About3. Although the order of addition is not critical, but currently prefer adding HNO3to the aqueous slurry Sb2About3. Oxide or itrate bismuth and uranium can be added together or separately in any order. Currently I prefer to add oxides or nitrates of bismuth before adding oxides or nitrates of uranium. Preferred in the present compounds bismuth and uranium oxide are bismuth (Bi2About3) and oxide-uranium oxide (U3O8). If you use the oxides of bismuth and uranium, we prefer to add the bismuth oxide, heating the suspension at a temperature of about 60°and then start adding oxide of uranium. If you are using nitrates of bismuth and uranium, they prefer not to heat the suspension until the addition of both components will not end.

The first mixture is heated to obtain a second mixture and to convert alpha-trioxide of antimony in beta antimony trioxide and other crystalline oxides of antimony, and at least part of antimony trioxide moves to higher levels of oxidation, for example, turns into cityregional and patikis antimony. The time required for the induction of the desired crystalline oxides of antimony, may vary and depends, at least in part, on the applied temperature. Usually a sufficient time interval within about 1-6 hours, preferably about 2-5 hours at a temperature of about 80-110°C.

After the heating period is completed in the second mixture, which is optionally cooled to a temperature of approx the positive 40-60° To add an aqueous solution of compounds of trivalent iron, preferably iron nitrate, Fe(NO3)3·N2O. the pH Value of the mixture regulate within 7-8 .5 with aqueous ammonia. The obtained hydrated mixture mixed oxides precipitate, which is then separated from the aqueous phase and washed thoroughly with for, if possible, completely remove all adsorbed impurities, in particular of ammonium nitrate. Subsequently, the sedimentary component of hydrated mixed oxide again resuspended to obtain a water suspension.

The composition of the sedimentary component of hydrated mixed oxide molybdate you can enter any connection that does not affect the process of catalysis or not will neutralize the catalyst. For the introduction of molybdate was successfully used ammonium molybdate, which is currently considered the best, being the easiest to obtain (from molybdenum trioxide and aqueous ammonia).

The catalyst described in this invention can be used with the carrier without it. In some applications prefer to include in the catalyst material of the carrier, which provides more reactive catalytic surface, forming a more solid and durable catalyst for use in the abrasive okrujaiushaia reactor with a fluidized bed of catalyst. The material of the carrier may be any of the commonly proposed for such use substances, such as quartz, zirconium dioxide, alumina, alumina, titanium dioxide, colloidal solution of antimony pentoxide or other oxide substrate. From the point of view of availability, cost and operation of the quartz is usually satisfactory material as the carrier and is preferably in the form of easily dispersible Zola silica.

Ratios involving components of the catalyst on an inert carrier, can vary within wide limits, but generally prefer the content of the media about 10-90 weight percent, more preferably about 35-65 weight percent, most preferably 45-55 weight percent, of the total combined weight of catalyst and carrier. To enable the carrier in the catalyst material carrier along with molybdate include suspension of the sedimentary component of hydrated mixed oxide with the appropriate pH value and while maintaining the fluidity of the suspension. When the material of the carrier is basic, the pH may be approximately 7-9. When the material of the medium is acidic, type acidic Sol of silica, it is desirable suspensions with low pH value (pH<4). Preparation of suspension will depend on the specifics of the used is on material media, and these conditions will be apparent to a skilled specialist.

The resulting suspension is ground, for example, using a ball mill for a time sufficient for grinding solid particles up to the size of diameter less than 10 microns. Typically, the grinding time of the suspension is approximately 20 hours. Then, if necessary, adjust the pH of the suspension within about 8-9.

If desired, the crushed slurry can be heated to the appropriate temperature, for example approximately 95-105°and support for a suitable time, for example approximately 2-6 hours. If the suspension is heated, the heated suspension is ground a second time as described above. If desired, before grinding, the heated slurry may be arbitrarily chilled.

At this stage, the thoroughly mixed slurry is dried and calicivirus as described above, resulting in a gain described in this invention the catalyst.

The catalyst described in this invention can be used to ammoxidation and oxidation of olefins.

Ammoxidation

According to this invention can be amoxicilline a wide range of different reagents, resulting in formation of NITRILES. For example, according to this invention, olefins, such as propylene, isobutylene, 2-m is l-1-penten, 1,4-hexadiene and other alcohols, such as methanol, tert-butyl alcohol and aldehydes, such as acrolein and methacrolein, can be easily converted to NITRILES. Compounds that result from the reaction of ammoxidation with the use of the catalyst described in this invention is usually easily converted into NITRILES include hydrocarbons having 1-9 carbon atoms, unsubstituted or substituted by oxygen or hydroxyl group. The preferred starting material are olefins, aldehydes and alcohols containing 1-4 carbon atoms.

Basically the way ammoxidation for the conversion of olefins, alcohols and aldehydes to NITRILES is well known. See, for example, U.S. patent No. 3546138, the content of which is incorporated here by reference. The reaction ammoxidation mainly carried out by the interaction of the reagent, oxygen and ammonia in the presence of a specific catalyst in the vapor phase. In General, the reaction can be performed according to the method and conditions described in this invention.

The most frequently applied methods of ammoxidation mixture of olefin, ammonia and oxygen (or air) is fed into the reactor through a layer of catalyst particles at high temperatures. The values of these temperatures usually range from approximately 400°With up to approximately 550°C, preferably in the range from about 425°to the roughly 500° C and the pressure is about 1 to 6 atmospheres (approximately 100 to 600 kPa). Required stoichiometric or equimolar amounts of ammonia and olefin, but usually, to reduce the possibility of adverse reactions, it is necessary to operate at a molar ratio of ammonia to olefin above 1. Similarly, the stoichiometric oxygen demand 1.5 times higher than the molar number of the olefin. Usually the initial reaction mixture is fed into the catalyst bed at W/F (defined as the weight of catalyst in grams divided by the flow of reaction mixture (ml/s) at standard temperature and pressure) in the range of about 2-15 g/ml, preferably about 3-10 g/ml.

The reaction ammoxidation is exothermic, and for convenient distribution and heat removal catalyst layer, it is desirable to make the bed. However, alternative means of removing the heat can also be used catalysts pinned layer.

The catalyst prepared according to the method described in this invention, particularly well suited for use in such a process, because of its unique and new ways of preparing this catalyst improves the yields of the target product (target product) and the selectivity of its receipt.

Oxidation

As noted above, rolled the ATOR, described in this invention can be used also for the catalytic oxidation of olefins with the formation of different reaction products.

Reagents used for oxidation in oxygendemand compounds are oxygen and olefin, such as propylene, isobutylene and other olefins containing up to three adjacent carbon atoms (i.e. three carbon atoms, arranged in a straight chain).

The olefins can be in the form of mixtures of paraffin hydrocarbons, such as ethane, propane, butane and pentane; for example, a mixture of propylene and propane may be the initial reaction mixture. This allows the use of conventional ropinirole mixture without special training.

The temperature at which carry out the oxidation can vary significantly depending on the used catalyst, the specific oxidized olefin, from the correlated values of the flow rate of material flow through the system, or the duration of contact of the reactants and the ratio of olefin to oxygen. In General, preferably recommended to operate at pressures close to atmospheric, i.e. at 0.1-10 atmospheres in the temperature range 150-600°C. However, the process can be conducted at other pressures, and in the case of pressure above atmospheric, for example more than 10 atmospheres, you can use a few more than the low temperature. It was shown that if this process is used for the conversion of propylene to acrolein, at atmospheric pressure the temperature range 200-500°C is optimal.

At the same time as other than atmospheric may be used, and other pressure, generally prefer to work at atmospheric pressure or a pressure close to atmospheric, as at such pressures, the reaction proceeds well and use need for expensive high pressure equipment is not required. In addition, it reduces the formation of undesirable by-products and waste.

The true contact time used in the process is not critical and may be selected from a wide current range, which can vary from 0.1 to 50 seconds. The true contact time can be defined as a period of time, in seconds, for which the volume units of gas, measured under the reaction conditions, is in contact with the true volume unit of catalyst. It can be calculated, for example, from the true volume of the catalyst layer, the temperature and pressure in the reactor and the flow rates of several components of the reaction mixture.

The optimum contact time will of course vary depending on the treated olefin, however, in the case of propylene and isobutylene are preferred contact time - 0.15-cakung.

The molar ratio of oxygen to olefin is in the range of approximately 0.5:1-5:1 and usually gives the most satisfactory results. For the conversion of propylene to acrolein, the preferred ratio of oxygen to olefin is about 1:1-2:1. The oxygen used in the way that you can get from any source; however, the air is the least expensive source of oxygen, and for this reason is preferred.

In the reaction mixture may be inert diluents such as nitrogen and carbon dioxide.

When carrying out the above processes ammoxidation and oxidation can be used any apparatus suitable for carrying out oxidation reactions in the vapor phase. The processes can be carried out, or continuously, or periodically. The catalyst may be fixed layer, it is possible to use a catalyst with large particles or granular catalyst or, alternatively, you can use the catalyst fluidized bed.

To facilitate understanding of the present invention, described in the following examples illustrating the invention. However, it should be noted that these examples with a description of preferred implementations are given for illustration only and should not be considered as limiting the invention, as after reading the description of the invention Spa is ialist will become apparent, various changes and modifications within the entity of the present invention.

EXAMPLES

Abbreviations and source material

Sb2About3- antimony trioxide great lakes chemical (Great Lakes Chemical)

HNO3- nitric acid, 70%, A.C.S. reactive extent the VWR Scientific products (VWR Scientific Products)

U3O8oxide-uranium oxide - Starmet Corporation (Starmet Corporation)

Bi2O3oxide of bismuth - ferro Corporation (Ferro Corporation)

NH4OH - ammonium hydroxide, 28%, A.C.S. reactive extent the VWR Scientific products (VWR Scientific Product)

Fe(NO3)3- ferric nitrate, 7% Fe solution Bluegrass chemical (Bluegrass Chemicals)

SiO2the silica Sol - Ondeo NACO (Ondeo Naico)

Moo3- trioxide of molybdenum - Climax Molybdenum (Climax Molybdenum)

The terms used here are defined as follows.

1. "W/F" is defined as the weight of catalyst in grams divided by the flow of reaction mixture (ml/s) defined in the STP, units are expressed in g/ml.

2. "Conversion of propylene (C3H6)" is defined as moles3H6in the feed solution - moth3H6in facing the solution ×100 moles3H6in the feed solution.

3. "Selectivity of Acrylonitrile (AN)" is defined as moles'AN in the feed solution ×100 moles3H6in the converted output solution.

4. "The output of Acrylonitrile (AN)" is defined as the mole on Razumova AN_× 100 moles3H6in facing the solution.

5. "Index of catalytic activity (CAI)" is defined as

-{ln[l-(% conversion/100)]}×100/weight of catalyst.

Evaluation of the catalysts of examples 1-6 to determine the selectivity of Acrylonitrile, output and conversion of propylene was carried out in the reaction vessel fluidized bed with an inner diameter of approximately 41 mm, the Amount of catalyst used for the evaluation was within 360-440 g and was adjusted to obtain the conversion of propylene between 98.5-99.2%. The reaction mixture of 7.7 mole percent propylene (C3H6), 8.4 mole percent of ammonia (NH3and balanced air is passed upward through the catalyst bed at a rate sufficient to obtain the desired values of W/F. the temperature of the catalyst layer was maintained at 460°and the pressure is approximately 207 kPa (30 psi).

All reactions for the preparation of the catalyst was carried out in a reactor made of stainless steel, covered in heat-insulating casing (˜10 l), using the heat exchanger high temperature and stirrer with variable speed (cutting blade stirrer without the guide walls). In the examples of the present invention HNO3served with a controlled rate using a peristaltic pump system Kaul-Farmer Master the Lex (Cole-Farmer Masterflex® ) of the conductive line Norrin (Norprene®) 16. The time of submission of HNO315 minutes corresponded to the feed speed 48.2 ml/min, feed HNO330 minutes corresponded to the feed rate of 24 ml/minute and the time of submission of HNO345 minutes corresponded to the feed rate of 16 ml/minute.

Example 1

The catalyst composition U1Fe2.03Sb5.63Mo0.12Bi0.061Of- 50% SiO2was prepared as follows. The reactor was loaded 1324 g of water and put the mixer at 210 rpm In the reactor was loaded 590 g Sb2About3and when you are finished adding Sb2About3the contents of the reactor were stirred for 30 minutes. Pump for download HNO3was activated for 15 min, and mixing conditions in the reactor was loaded with 1020 g of HNO3. After the download is complete, HNO3the reactor was loaded 10.2 g of Bi2O3. The contents of the reactor were heated at 58-60°C. After the temperature of the reactor reached 60°With the temperature controller was set at 88°and in the reactor was loaded 201.8 g U3O8. After the download is complete, U3About8the temperature of the contents of the reactor was raised to 100°and the contents of the reactor were maintained at a temperature of 100°C for 4 hours. Heating of the reactor was stopped and through the reactor vessel was omitted cold water, and the reaction is EO downloaded 1135 g of deionized (DI) of ice. When the temperature of the contents of the reactor reached 52°C, the reactor was loaded 1166 g chilled solution of Fe(NO3)3. After the download is complete, Fe(NO3)3the contents of the reactor were cooled to 32°C. was prepared solution of NH4OH (1349 ml of 28% NH4OH/1051 ml of N2O) and NH4HE was loaded into the reactor with the aim of uregulirovania pH. The time when the pH of the contents of the reactor reached 5, was registered, was added 189 g H2O and the pH was maintained for 15 minutes After a 15 minute exposure was resumed adding NH4OH until the pH is not reached 8. Once the pH reached 8 was added 3026 g H2Oh and the speed of the stirrer of the reactor was reduced to 100 rpm, the Reactor was left for the night.

The precipitate of hydrated mixed metal oxide was separated from the mother liquor by vacuum filtration, the obtained wet cake was resuspending in 20 liters of deionized water and again filtered to remove the formed during the precipitation of the ammonium nitrate.

3300 g of the washed filtered mass was mixed with 2337 g Zola SiO2and 3.4 weight percent solution of molybdenum prepared by dissolving 12.05 g of Moo3in dilute NH4OH (37 ml of 28% NH4OH/187 ml of N2About). To reduce the concentration of solid particles in suspension up to 25 weight percent was EXT is established with representation from additional water. The suspension was milled in a ball mill for 20 hours and dried by a spray method at a temperature output 83-85°C. then dried by spraying the particles were calcined at 400°C for 1 hour, then at 850°C for 1 hour, resulting received the target catalyst.

Example 2

The catalyst composition U1Fe2.03Sb5.63Mo0.12Bi0.061Of- 50% SiO2was prepared according to the procedure described in example 1, except that the original speed of the stirrer of the reactor was 180 rpm, the pump speed to download HNO3was set at 30 min, and after addition of Fe(NO3)3the speed of the stirrer of the reactor was increased to 210 rpm

Example 3

The catalyst composition U1Fe2.03Sb5.63Mo0.12Bi0.061Of- 50% SiO2was prepared according to the procedure described in example 1, except that the original speed of the stirrer of the reactor was 150 rpm, the pump speed to download HNO3was set to 45 min, and after addition of Fe(NO3)3the speed of the stirrer of the reactor was increased to 210 rpm

Example 4

The catalyst composition U1Fe2.03Sb5.63Mo0.12Bi0.061Of- 50% SiO2was prepared according to the procedure described in example 1, except the rising, the pump speed to download HNO3was set at 45 minutes

Example 5

The catalyst composition U1Fe2.03Sb5.63Mo0.12Bi0.061Of- 50% SiO2was prepared according to the procedure described in example 1, except that the original speed of the stirrer of the reactor was 150 rpm, and after adding Fe(NO3)3the speed of the stirrer of the reactor was increased to 210 rpm

Example 6 (control)

The catalyst composition U1Fe2.03Sb5.63Mo0.12Bi0.061Of- 50% SiO2was prepared as follows. The reactor was loaded 1020 g of HNO3and 10.2 g of Bi2O3and included a stirrer at 60 rpm After that, the contents of the reactor were heated at 58-60°C. After the temperature of the reactor reached 60°With the temperature controller was set at 88°and in the reactor was loaded 201.8 g U3O8. After the download is complete, U3O8the temperature of the contents of the reactor was maintained in the range of 90-95°C for 30 min. In the reactor was loaded 1324 g of water, the contents of the reactor was again heated at 90-95°and the speed of the stirrer of the reactor was increased to 150 rpm In the reactor was loaded 590 g of powdered Sb2O3. After the download is complete Sb2O3the temperature of the contents of the reactor was raised to 100°and the contents of the reactor which was heated at this temperature for 4 hours Heating of the reactor was stopped and through the reactor vessel was omitted cold water, and the reactor was loaded 1135 g of deionized (DI) of ice. When the temperature of the contents of the reactor reached 52°C, the reactor was loaded 1166 g chilled solution of Fe(NO3)3. After the download is complete, Fe(NO3)3the speed of the stirrer of the reactor was increased to 210 rpm and the contents of the reactor were cooled to 32°C. was prepared solution of NH4OH (1349 ml of 28% NH4OH/1051 ml of N2O) and NH4HE was loaded into the reactor with the aim of uregulirovania pH. The time when the pH of the contents of the reactor reached 5, was registered, was added 189 g H2O, and the pH was maintained for 15 minutes After a 15 minute exposure was resumed adding NH4OH until the pH is not reached 8. Once the pH reached 8, was added 3026 g H2O and the speed of the stirrer of the reactor was reduced to 100 rpm, the Reactor was left for the night.

The precipitate of hydrated mixed metal oxide was separated from the mother liquor by vacuum filtration, the obtained wet cake was resuspending in 20 liters of deionized water and again filtered to remove the formed during the precipitation of the ammonium nitrate.

3140 g of the washed filtered mass was mixed with 2499 g Zola SiO2and 3.4 weight percent solution of molyb is s, prepared by dissolving 12.74 g of Moo3in dilute NH4OH (40 ml of 28% NH4OH/198 ml of N2O). To reduce the concentration of solid particles in suspension up to 25 weight percent was added water. The suspension was milled in a ball mill for 20 hours and dried by a spray method at a temperature output 83-85°C. then dried by spraying the particles were calcined at 400°C for 1 hour, then at 850°C for 1 hour, resulting received the target catalyst.

All of the suspension obtained in the reactor according to the method of the present invention (examples 1-5)were more homogeneous than those obtained in the reactor control suspension (example 6).

Example 7

The efficiency of the catalysts of examples 1-6 in the process of ammoxidation propylene (C3H6in Acrylonitrile was investigated by conducting the reaction of ammoxidation according to the procedure described above. The parameters for the reaction of ammoxidation are given in table 1. Was determined the activity of the catalysts and the results are shown in table 2.

Table 1
Catalyst1 (image)2 (Fig)3 (Fig)4 (Fig)5 (image)6 (the STD)
The reaction temperature, °460460460460460460
The pressure of reaction, ×102kPa2,072,072,072,072,072,07
The molar percentage of the supplied mixture, %
With3H47,77,77,77,77,77,7
NH38,48,48,48,48,48,4
The airBalancer.Balancer.Balancer.Balancer.Balancer.Balancer.
W/F, g-sec/ml3,3393,7233,4063,6423,6544,120

Table 2
ExampleAdd HNO3, minMixing RPMOutput

CO%
The output of C2O%The release of HCN,% Put AN %Output'AN, %Converted

With3H4, %
CAIPut the mixture weight (g)
1 (invention)151504,90to 6.887,2579,6678,8899,031,189390
2 (invention)15210a 4.835,987,1580,6879,5698,611,189360
3 (invention)30180is 4.936,777,4979,3978,5098,881,110 land only405
4 (invention)451504,576,457,3180,2079,2198,761,220360
5 (invention)45210to 4.98to 6.197,1280,6779,6998,781,146385
6 (control)N/A60/150/2105,137,007,3079,2878,5599,091067 440

The results in table 2 demonstrate that the catalysts described in the invention have a higher'AN selectivity and more active, i.e. have a higher CAI than the control catalyst, i.e. the catalyst described in the invention, using additive Sb2About3in suspension are improved compared with the control catalyst. In addition, compared with control, improved outputs co and CO2.

To determine whether there were any differences in the compositions of the crystalline oxide target of the catalyst, the catalysts of examples 1-6 were analyzed using x-ray diffraction (XRD) using a reference XRD instrument Philips APD 3600 (Philips APD 3600), which was equipped with electronics APD 3710.

Crystalline phase αSb2About3observed in the control catalyst (example 6) is expressed more clearly than in all the catalysts of the invention (examples 1-5). Relative to a reference catalyst (example 6), the catalysts of this invention show elevated levels of AN active phase of antimonate, FeSbO4, USbO5and USb3About10and a decrease in the crystalline phase αSb2O3.

1. The method of preparation of the mixed metal oxide catalyst based antimonate in a catalytically active oxidized when standing; the specified catalyst has the empirical formula:

MeaSbbXcQdReOf,

where Me is at least one element from the group of Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th, Ce, Pr, Sm or Nd; X is at least one element from the group of V, Mo, or W; Q is at least one element from the group of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Y, La, Zr, Hf, Nb, TA, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Tl, Ge, Pb, As, or Se; R is at least one element from the group of Bi, In, P, or Te; and the indices a, b, C, d, e, and f represent atomic relations: a has a value from 0.1 to 15; b has a value from 1 to 100; C is from 0 to 20; d has values from 0 to 20; e is from 0 to 10; and f is a number taken to satisfy the valence requirements of the metals corresponding to the degree of oxidation, which they have in the composition of the catalyst; the method includes:

(a) the contact of the aqueous suspension Sb2About3from HNO3and with one or more compounds Me, and arbitrary, with one or more compounds from the group: X, Q, or R, to obtain a first mixture;

(b) heating and drying the specified first mixture, resulting in a solid product; and

(c) calcining the specified solid product for the education of the specified catalyst.

2. The method according to claim 1, characterized in that it further includes adding to this first mixture, drying the specified PE the howl of the mixture, material carrier selected from the group of silica, zirconium dioxide, aluminum oxide or titanium dioxide, in an amount such that the specified catalyst contained the material of the carrier in an amount of about 10-90% of the total mass of the specified catalyst.

3. The method according to claim 2, characterized in that the catalyst contains about 35-65 wt.% the specified material of the carrier to the total weight of the specified catalyst.

4. The method according to claim 3, characterized in that the material of the carrier is a silica Sol.

5. Mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, this catalyst produced according to the method described in section 2.

6. The method according to claim 1, characterized in that matter from 0.01 to 10, and e has a value from 0.01 to 5.

7. The method according to claim 5, wherein Me is selected from Fe, Co, Ni, Sn, U, Cr, Cu, Mn, Ti, Th or CE; and R is selected from Bi, Te or R.

8. The method according to claim 7, characterized in that the MEA contains Fea and Ua′and and and and′ independently selected from 0.1 to 10.

9. The method according to claim 8, characterized in that R is Bi, and X represents Mo.

10. The method according to claim 9, characterized in that the catalyst represented by the empirical formula:

Ua′FeaSbbMocBieOf,

where a and a′ illegal is isimo selected from 0.1 to 5, b has a value from 1 to 10, p has a value from 0.001 to 0.2, and e has a value from 0.001 to 0.2.

11. Mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, this catalyst produced according to the method described in item 10.

12. The method according to claim 1, characterized in that the temperature of calcination is in the range of approximately 500-1150°C.

13. The method according to item 12, characterized in that the temperature of calcination is in the range of approximately 600-900°C.

14. Mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, this catalyst produced according to the method described in claim 1.

15. The method of preparation of the mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, this catalyst has the empirical formula:

Ua′FeaSbbMocBieOf,

where the indices a, and′a, b, C, e, and f represent atomic relations: a has a value from 0.1 to 5; and′ has a value from 0.1 to 5; b has a value from 1 to 10; C has a value from 0.001 to 0.2; e has a value from 0.001 to 0.2; and f is a number taken to satisfy the valence requirements of Sb, U, Fe, Bi, and Mo, corresponding to the degree of oxidation, they are part of the catalysate is RA;

the method includes:

(a) the contact of the aqueous suspension Sb2About3from HNO3, oxides or nitrates of bismuth and oxides or nitrates of uranium for the formation of the first mixture;

(b) heating the specified first mixture at a temperature and for a time sufficient to induce formation of the desired crystalline oxides of antimony and form a second mixture;

(c) adding an aqueous solution of compounds of trivalent iron to the said second mixture for formation of the third mixture;

(d) adjusting the pH of the specified third of the mixture within about 7-8,5, and formation of a precipitate of hydrated mixed oxide in the aqueous phase;

(e) separating the precipitate of hydrated mixed oxide from the aqueous phase;

(f) formation of aqueous suspension of the sedimentary component of hydrated mixed oxide;

(g) the addition of molybdate to the suspension component of hydrated mixed oxide;

(h) formation of a suspension of hydrated mixed oxide-molybdates component in the form of dry particles; and

(i) calcining the dry particles for the formation of the catalyst.

16. The method according to item 15, wherein a has a value from 0.1 to 1, and′ has a value from 0.1 to 1, b has a value from 1 to 5, p has a value from 0.01 to 0.1, and e has a value from 01 to 0.05.

17. Mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, this catalyst produced according to the method described in item 16.

18. The method according to item 15, wherein the specified first mixture is formed of bismuth trioxide and oxide-oxide of uranium.

19. The method according to p, characterized in that the third mixture is formed from ferric nitrate.

20. The method according to item 15, wherein the specified first mixture is heated at a temperature of about 80°C-110°C for a time of approximately 1-6 hours

21. The method according to item 15, wherein the molybdate is ammonium molybdate.

22. The method according to item 15, characterized in that it further includes adding a support material selected from oxides of silicon, zirconium, aluminum or titanium, to the suspension of hydrated mixed oxide molybdates component, where the specified catalyst contains the specified material of the carrier in an amount of about 10-90% of the total mass of the specified catalyst.

23. The method according to item 22, characterized in that the catalyst contains about 35-65 wt.% the specified material of the carrier to the total weight of the specified catalyst.

24. The method according to item 22, wherein the material of the carrier is a Sol-flint the EMA.

25. The method according to item 22, wherein the material of the carrier is added to the suspension of hydrated mixed oxide component to add the specified molybdate.

26. Mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, this catalyst produced according to the method described in article 22.

27. The method according to item 15, characterized in that the said dry particles are formed by spray drying aqueous suspension.

28. The method according to item 15, wherein the temperature of calcination is in the range of approximately 500-1150°C.

29. The method according to item 15, wherein the specified temperature of calcination is in the range of approximately 600-900°C.

30. Mixed metal oxide catalyst based antimonate in a catalytically active oxidized state, this catalyst produced according to the method described in item 15.



 

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30 cl, 1 dwg, 3 ex

FIELD: chemical industry; petrochemical industry; methods (versions) of the ammoxidation of the carboxylic acids in the mixture of nitriles.

SUBSTANCE: the invention is pertaining to the methods (versions) of the ammoxidation or to the method of increasing of the yield of the acetonitrile in the form of the by-product produced in the process of manufacture of acrylonitrile, which provide for injection of the reactants, which contain at least one hydrocarbon selected from the group, which includes propylene and the propane, at least one С1-С4 carboxylic acid, ammonia and the gas containing the molecular oxygen, into the reaction zone containing the catalyst of the ammoxidation, and realization of the reaction of the indicated reactants above the indicated catalyst at the heightened temperature with production of the yield, which contains acrylonitrile, hydrogen cyanide and acetonitrile. The method may additionally include the contact of the effluent of the reaction zone with the liquid of extinguishing, which contains the water and at least one С14 carboxylic acid, and the addition of at least a part of the extinguishing liquid into the reaction zone after the extinguishing liquid contacting the liquid of the reaction zone. The invention allows to increase the yield and, predominantly, the ratio of the by-product - acetonitrile to the acrylonitrile produced in the process of the ammoxidation of the hydrocarbon, such as propylene or propane into acrylonitrile.

EFFECT: the ensures the increased yield and the ratio of the by-product - acetonitrile to the acrylonitrile produced in the process of the ammoxidation of the hydrocarbon, such as propylene or propane into acrylonitrile.

22 cl, 1 tbl, 1 ex

The invention relates to an improved method for the recovery and regeneration of unreacted ammonia from the resulting stream containing Acrylonitrile or Methacrylonitrile derived from the reaction zone, where oxygen, ammonia and a hydrocarbon selected from the group consisting of propane and isobutane, interact in a reactor in the presence of a fluidized bed of ammoxidation catalyst at elevated temperature to obtain the corresponding unsaturated nitrile cooling discharge flow from the fluidized bed reactor containing the corresponding nitrile and unreacted ammonia from the first aqueous solution of ammonium phosphate, in which the ratio of ammonium ions (NH+4) to phosphate ions (PO-34) is from about 0.7 to about 1.3, to absorb essentially all of the unreacted ammonia present in stemming the flow reactor for the formation of the second aqueous solution of ammonium phosphate, richer ammonium ions than the first solution, heating the second aqueous solution of ammonium phosphate to elevated temperature sufficient to reduce the amount of ammonium ions in the second solution to essentially the same level present in n the th ammonia, in a fluidized bed reactor
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