Acrylonitrile production catalyst

FIELD: chemistry.

SUBSTANCE: present invention pertains to versions of catalyst compositions for ammonolysis of an unsaturated hydrocarbon into an unsaturated nitrile and to the method of converting olefin using such a catalyst. In the first version, the catalyst composition is a complex of catalytically active oxides, comprising oxides of potassium, caesium, cerium, chrome, cobalt, nickel, iron, bismuth and molybdenum, in which the ratio of elements is presented in the following general formula: AaKbCscCedCreCOfNigFeiBijMo12Ox. In this formula, A is Rb, Li or their mixture, a assumes values from 0 to 1, b assumes values from 0.01 to 1, c assumes values from 0.01 to 1, d assumes values from 0.01 to 3, e assumes values from 0.01 to 2, f assumes values from 0.01 to 10, g assumes values from 0.1 to 10, i assumes values from 0.1 to 4, j assumes values from 0.05 to 4, x is a number, defined by the valency of other elements present. In the second version, the catalyst composition is a complex of catalytically active oxides, comprising oxides of potassium, caesium, cerium, chrome, cobalt, nickel, iron, bismuth and molybdenum, in which the ratio of elements is presented in the following general formula: AaLia'KbCscCedCreCofNigFeiBijMo12Ox. A is Rb, a assumes values from 0 to 1, a' assumes values from 0.01 to 1, b assumes values from 0.01 to 1, c assumes values from 0.01 to 1, d assumes values from 0.01 to 3, e assumes values from 0.01 to 2, f assumes values from 0.01 to 10, g assumes values from 0.1 to 10, i assumes values from 0.1 to 4, j assumes values from 0.05 to 4, x is a number, defined by the valency of other elements present. In these given versions, the catalyst does not contain manganese and zinc and is put onto a carrier, selected from a group containing silica gel, aluminium oxide, zirconium oxide, titanium oxide or their mixture. The method of converting olefin into acrylonitrile, methacrylonitrile and their mixture involves reacting olefin with a gas, containing molecular oxygen or ammonia in vapour phase, in the presence of the above mentioned catalyst. The olefin used is propylene, isobutylene or their mixture.

EFFECT: invention allows for obtaining a catalyst with high activity and increases output of nitriles.

14 cl, 1 tbl, 3 ex

 

The present invention relates to a catalyst for the oxidative ammonolysis of unsaturated hydrocarbons to the corresponding unsaturated nitrile. In particular, the present invention is directed to an improved method and catalyst of oxidative ammonolysis of propylene and/or isobutylene to Acrylonitrile and/or Methacrylonitrile respectively. More specifically the invention relates to a new and improved catalyst for the oxidative ammonolysis containing complex catalytically active oxides of potassium, cesium, cerium, chromium, cobalt, Nickel, iron, bismuth and molybdenum in the practical absence of manganese and zinc.

Description of the prior art,

Catalysts containing the oxides of iron, bismuth and molybdenum promoted bets, have long been used for the conversion of propylene at elevated temperatures in the presence of ammonia and oxygen (usually air) in the production of Acrylonitrile. In particular, the United Kingdom patent No. 1436475; U.S. patent№№ 4766232; 4377534; 4040978; 4168246; 5223469 and 4863891 reveal the bismuth-molybdenum-iron catalysts for the production of Acrylonitrile which can be promoutirovanie elements of Group II. In addition, U.S. patent No. 4190608 offers similarly promoted bismuth-molybdenum-iron catalyst for the oxidation of olefins. U.S. patent No. 5093299, 521217, 5658842 and 5834394 dedicated bismuth-molybdenum-promoted catalysts receipt of Acrylonitrile with large outputs.

The aim of the present invention to provide a novel catalyst comprising a unique combination of promoters, leading to increased activity in the catalytic oxidative ammonolysis of propylene, isobutylene or mixtures thereof to Acrylonitrile, Methacrylonitrile and their mixtures, respectively.

The invention

The present invention is directed to an improved catalyst and method of oxidative ammonolysis of propylene and/or isobutylene to Acrylonitrile and/or Methacrylonitrile respectively.

In one embodiment the object of the invention is a catalyst comprising a catalytically active complex oxides, including oxides of potassium, cesium, cerium, chromium, cobalt, Nickel, iron, bismuth, molybdenum, in which the ratio of the elements represented by the following General formula:

AaKbCscCedCreCofNigFeiBijMo12Ox,

in which a represents a Rb, Li, or a mixture thereof,

a is from 0 to 1,

b is equal to from 0.01 to 1,

with equal to from 0.01 to 1,

d is equal to from 0.01 to 3,

e is equal to from 0.01 to 2,

f is equal to from 0.01 to 10,

g is equal to from 0.1 to 10,

i equal to from 0.1 to 4,

j is from 0.05 to 4

x represents the number of the Oh, determined by the valence requirements of the other elements present, and the catalyst does not contain significant amounts of manganese and zinc.

Another object of the present invention is a method of conversion of olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to Acrylonitrile, Methacrylonitrile or mixtures thereof, respectively, by reacting in the vapor phase at elevated temperature and pressure specified olefin with a gas containing molecular oxygen and ammonia in the presence of a mixed metal oxide catalyst, which is described above.

Detailed description of the invention

The new catalyst according to the present invention is a unique combination and ratio of promoters, leading to higher catalytic activity in the oxidative ammonolysis of propylene, isobutylene or mixtures thereof in Acrylonitrile, Methacrylonitrile or their mixture, respectively.

The catalyst is a catalytically active complex oxides, including oxides of potassium, cesium, cerium, chromium, cobalt, Nickel, iron, bismuth, molybdenum, in which the ratio of the elements represented by the following General formula:

AaKbCscCedCreCofNigFeiBijMo12Ox,

in which a represents a Rb, Li or with whom thou,

a is from 0 to 1,

b is equal to from 0.01 to 1,

with equal to from 0.01 to 1,

d is equal to from 0.01 to 3,

e is equal to from 0.01 to 2,

f is equal to from 0.01 to 10,

g is equal to from 0.1 to 10,

i equal to from 0.1 to 4,

j is from 0.05 to 4

x is a number determined by the valence requirements of the other elements present, and the catalyst does not contain significant amounts of manganese and zinc.

The indices in the formula indicate the possible intervals of the ratios of the individual elements relative to molybdenum. The person skilled in the art know that any composition of the catalyst total metals based on their oxidation States should be maintained in balance with molybdenum.

In one embodiment of the invention, the number (at the atomic level) of cerium plus chromium greater than the number of bismuth (i.e. "b"+"C" is greater than "g"). In another embodiment, the number (at the atomic level) of cerium is greater than the number of chromium (i.e. "b" is greater than "C"). In other embodiments, "a" ranges from about 0.05 to about 0.5, b is from about 0.01 to about 0.3, with from about 0.01 to about 0.3, "d." from about 0.01 to about 3, "f+g" from about 4 to about 10, "i" is from about 1 to about 3, and "j" from about 0.1 to about 2.

The main composition of the catalyst according to the invention is a complex catalytically active oxides of potassium, cesium, cerium, HRO is a, cobalt, Nickel, iron, bismuth and molybdenum. Except where specifically excluded items in it, you can add other elements or promoters. In one embodiment the catalyst may include one or more elements of rubidium, lithium, antimony, tellurium, boron, germanium, tungsten, calcium, magnesium and rare earth element (defined as one of the elements La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb). In yet another embodiment the catalyst contains rubidium (i.e. "A" represents at least Rb and "a" is greater than zero). In yet another embodiment, the catalyst does not contain rubidium. In yet another embodiment the catalyst contains lithium (i.e. "A" represents at least Li and "a" is greater than zero). In yet another embodiment the catalyst contains lithium and the ratio of lithium to molybdenum is in the range from about 0.01:12 to about 1:12 (i.e., where "A" represents one of Li, then "a" is equal to from about 0.1 to about 1). In the case of mixed oxide catalysts containing iron, bismuth and molybdenum, used for oxidative ammonolysis of propylene to Acrylonitrile, a combination of cobalt and lithium as an additional promoters leads to increased output NITRILES, such as Acrylonitrile, acetonitrile and hydrogen cyanide (also called formonitrile). In yet another embodiment, the catalyst does not contain a significant amount is in strontium and preferably, so he was completely absent. As indicated here, the term "does not contain substantial quantities" in relation to any item means that the catalyst is not generally contain any of the specified elements.

In addition, it was found that the introduction of certain elements in the catalyst, the conversion of propylene, ammonia and oxygen to Acrylonitrile has a negative impact on the yield of Acrylonitrile. These elements are manganese and zinc. Introduction manganese and zinc in the catalyst leads to a less active catalyst and lowers the yield of Acrylonitrile. Thus, the catalyst of the present invention do not contain significant amounts of manganese and zinc. With respect to manganese, this means that the atomic ratio of manganese to molybdenum of less than 0.1:12. In relation to zinc means that the atomic ratio of zinc to molybdenum of less than 1:12. Preferably, the catalyst does not contain manganese and/or zinc.

The catalyst according to the present invention can be used inflicted or nenalezena (i.e., the catalyst may contain a carrier). If you use the media, it is usually mixed with metal oxides included in the catalyst or the carrier can be impregnated with metal oxides. Suitable carriers are the oxides of silicon, aluminum, zirconium, titanium or mixtures thereof. Usually the media is wasysym to obtain a catalyst of greater hardness and resistance to abrasion. However, for industrial applications suitable mixture of the active phase (i.e. complex catalytically active oxides described above) and the media plays a crucial role in obtaining a catalyst with the desired activity and hardness (abrasion resistance). The increase in the number of active phases leads to an increase in the activity of the catalyst, but reduces its hardness. Typically, the carrier is from 40 to 60 wt.% the deposited catalyst. In one embodiment of the present invention the carrier may be only about 30 wt.% the deposited catalyst. In another embodiment of the present invention, the carrier may comprise up to about 70 wt.% the deposited catalyst.

In one embodiment the catalyst is applied using Sol of silica. If the average diameter of the colloidal particles of the specified Zola silica is too small, the catalyst will have a large value of the surface and the catalyst will be reduced selectivity. If the diameter of the colloidal particles is too large, the catalyst will have a low resistance to abrasion. Typically the average diameter of the colloidal particles Zola silica is in the range from about 15 nm to about 50 nm. In one embodiment of the present invention, the average diameter of the colloidal particles Zola silica is about 10 nm and can be is even equal to about 8 nm. In another embodiment of the present invention, the average diameter of the colloidal particles or Sol of silica is approximately 100 nm. In yet another embodiment of the invention, the average diameter of the colloidal particles or Sol of silica is approximately 20 nm.

The catalysts according to the present invention can be prepared by one of the numerous ways of preparation of the catalysts known to specialists in this field. For example, the catalyst can be obtained by coprecipitation of the various ingredients. Then soosazhdenie mass can be dried and crushed to the desired particle size. Or soosazhdenie substance can be suspended and dried by spraying according to traditional methods. The catalyst can be ekstradiroval in the form of tablets or molded in the form of balls in oil, as is well known in the art. Examples of preparation of the catalyst, see U.S. patent No. 5093299, 4863891 and 4766232. In one embodiment of the components of the catalyst can be mixed with a carrier in the form of a suspension and then dried or components of the catalyst can be impregnated with silica or other media.

Bismuth can be introduced into the catalyst in the form of oxides or salts, which, after annealing to form the oxide. It is preferable to use water-soluble salts, which are easily dispersed, but after heat treatment to form stable oxides. Especially predpochtitel the first source for introducing bismuth is bismuth nitrate.

Iron can be introduced into the catalyst in the form of any compound that, after annealing will turn into oxides. Other elements preferably in the form of water-soluble salts, as in this case, is easily achieved with a uniform distribution in the catalyst. The most preferred ferric nitrate.

Molybdenum can be introduced into the catalyst from any oxide of molybdenum, for example dioxide, trioxide, pentoxide or heptoxide. However, it is preferable to use as the source of molybdenum salt, which is easily hydrolyzed and decomposed. The most preferred source of concern is heptamolybdate ammonium.

Other necessary components of the catalyst and optional promoters (for example, Ni, Co, Mg, Cr, P, Sn, Te, In, Ge, Zn, In, Ca, W, or mixtures thereof) can be entered from any suitable sources. For example, cobalt, Nickel and magnesium can be introduced into the catalyst in the form of nitrates. In addition, the magnesium can be introduced into the catalyst in the form of insoluble carbonate or hydroxide, which after heating will lead to oxide. Phosphorus can be introduced into the catalyst in the form of salts of alkali or alkaline earth metal or ammonium salts, but preferably in the form of phosphoric acid.

Required and optional alkaline components of the catalyst (for example, Rb, Li, Na, R, Cs, Tl or a mixture thereof) can be in order to introduce the catalyst in the form of oxides or salts, which upon annealing into the oxide. It is preferable to introduce these elements in the catalyst to use salt such as nitrate, which is readily available and highly soluble.

Typically, the catalysts are prepared by mixing an aqueous solution of heptamolybdate ammonium Sol of silica gel, to which is added a suspension of compounds, preferably nitrates, other elements. The solid is dried, denitrification and calcined. Preferably, the catalyst is dried by spraying at a temperature of from 110°With up to 350°C, preferably from 110°, 250°S, most preferably from 110°to 180°C. Temperature denitrification may be in the range from 100°500°C, preferably from 250°With up to 450°C. Finally, the calcination is carried out at a temperature of 300°With up to 700°C, preferably from 350°650°C.

The described catalysts applicable in the processes of oxidative ammonolysis for the conversion of olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to Acrylonitrile, Methacrylonitrile or mixtures thereof, respectively, by reaction in the vapor phase at elevated temperature and pressure specified olefin with a gas containing molecular oxygen and ammonia in the presence of a catalyst.

It is preferable to conduct the reaction of oxidative ammonolysis of the reaction is the PR fluidized bed, although you can use other reactor types, for example, a reactor with a linear transfer. Reactors with a fluidized bed for the production of Acrylonitrile are well known. For example, a suitable reactor design proposed in U.S. patent No. 3230246.

Reaction conditions of oxidative ammonolysis is also well known, as it follows from the U.S. patent nos 5093299; 4863891; 4767878 and 4503001. Usually the process of oxidative ammonolysis is carried out by contacting propylene or isobutylene in the presence of ammonia and oxygen with a fluidized bed of catalyst at an elevated temperature to produce Acrylonitrile or Methacrylonitrile. You can use any source of oxygen. However, for economic reasons it is preferable to use the air. Usually the molar ratio of oxygen to olefin in the mixture should be in the range from 0.5:1 to 4:1, preferably from 1:1 to 3:1.

The molar ratio of ammonia to olefin in the initial reaction mixture can vary from 0.5:1 to 2:1. Generally the upper limit for the ammonia-olefin does not exist, but should not go beyond 2:1 for economic reasons. A reasonable ratio of components in the initial mixture for the reaction in the presence of the catalyst of the present invention to obtain Acrylonitrile from propylene are in the interval relations ammonia:about the ilen from 0.9:1 to 1.3:1 and relations air:propylene from 8.0:1 to 12.0:1. The catalyst of the present invention are getting high outputs of Acrylonitrile at relatively low relationship of ammonia to propylene in the original mixture from about 1:1 to about 1.05:1. Such conditions low ammonia content can help reduce the amount of unreacted ammonia in the exhaust gas reactor of the phenomenon known as "leakage of ammonia, which, in turn, helps to reduce harmful emissions. In particular, unreacted ammonia should be removed from the exhaust gases of the reactor to the stage of selection of Acrylonitrile. Usually unreacted ammonia is removed by contacting the waste gases with sulfuric acid to form ammonium sulfate or by contacting the waste gases with acrylic acid with the formation of ammonium acrylate that in both cases, provides the necessary processing and neutralization of harmful emissions.

The reaction is carried out at a temperature in the range of from about 260°to 600°C, preferably from 310°500°S, particularly preferably from 350°480°C. the contact Time, although not critical, is in the range from 0.1 to 50, the preferred contact time is from 1 to 15 C.

The reaction products can be extracted and cleaned by any method known to specialists in this field. One such method involves passing the exhaust gases is of eector through the scrubber with cold water or a suitable solvent, to remove the reaction products, and then purification by distillation.

The first purpose of the catalyst according to the present invention consists in the reaction of oxidative ammonolysis of propylene to Acrylonitrile. However, the present catalyst can also be used for the oxidation of propylene to acrylic acid. Such processes are typically two-stage; propylene in the first stage is first converted in the presence of a catalyst to acrolein and then in the second stage acrolein is converted in the presence of a catalyst in acrylic acid. Described in the invention, the catalyst is intended for use in the first stage for the oxidation of propylene to acrolein.

Examples of carrying out the invention

For illustration of the present invention were prepared with the catalyst according to the present invention, as well as a similar catalyst without one or more elements or, on the contrary, includes additional elements, adverse to obtain Acrylonitrile, and then they were tested under similar reaction conditions. These examples are for illustration purposes only.

Preparation of catalysts

Example 1

The catalyst of the formula 50 wt.% Cs0.1K0.1Ce0.75Cr0.3Co4.3Ni4.4Fe2.0Bi0.5Mo14.425About57.775+50 wt.% SiO2was prepared following the m follows: nitrates of metals CsNO 3(1.535 g), KNO3(0.796 g), Fe(NO3)39H2O (63.643 g), Ni(NO3)26H2O (100.778 g), Co(NO3)26H2O (98.572 g), Bi(NO3)35H2O (19.104 g) and (NH4)2CE(NO3)6(64.773 g of 50% solution) was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (200.603 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(2.363 g) in 20 ml of water. Then was added silica gel (625 g 40% Zola SiO2) and the melt of metal nitrates. The obtained yellow suspension was spray dried. The resulting substance was centrifically at 290°C/3 h and 425°C for 3 h and then was progulivali at 570°C for 3 h in air.

Example 2

Using the method described above in Example 1, a catalyst of the formula 50 wt.%

Cs0.1K0.1Li0.3Ce0.58Cr0.12Co5.3Ni3.1Fe1.8Bi0.62Mo13.744O54.852+50 wt.% SiO2was prepared as follows: nitrates of metals CsNO3(12.877 g), KNO3(6.679 g), LiNO3(13.665 g), Fe(NO3)39H2O (480.431 g), Ni(NO3)26H2O (595.542 g), With(NO3)26N2On (1019.059 g), Bi(NO3)35H2O (198.691 g) and (NH4)2CE(NO3)6(420.146 g of 50% solution) was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (1603.142 g) was dissolved in 1760 m is distilled water. To this solution was added a solution of CrO3(7.928 g) in 20 ml of water. Then was added silica gel (5000 g 40% Zola SiO2) and the melt of metal nitrates. The obtained yellow suspension was spray dried. The resulting substance was centrifically at 290°C/3 h and 425°C for 3 h and then was progulivali at 570°C for 3 h in air.

Comparative example A (no Ni). Using the method described above in Example 1, a catalyst of the formula 50 wt.% Cs0.1K0.1Ce0.75Cr0.3Co8.7Fe2.0Bi0.5Mo14.425O57.775+50 wt.% SiO2prepared from the following list: CsNO3(1.535 g), KNO3(0.796 g), Fe(NO3)3N2O (63.623 g), Co(NO3)26H2O (199.375 g), Bi(NO3)35H2O (19.098 g) and (NH4)2CE(NO3)6(64.753 g of 50% solution) was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (200.603 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(2.362 g) in 20 ml of water. Then was added silica gel (625 g 40% Zola SiO2) and the melt of metal nitrates.

Comparative example (without To). Using the method described above in Example 1, a catalyst of the formula 50 wt.% Cs0.2Ce0.75Cr0.3Co4.3Ni4.4Fe2.0Bi0.5Mo14.425O57.775+50 wt.% SiO2prepared from the following list: CsNO3(3.061 g), Fe(NO3 )39H2O (63.456 g), Ni(NO3)26N2On (100.481 g), Co(NO3)26H2O (98.282 g), Bi(NO3)35H2O (19.047 g) and (NH4)2CE(NO3)6(64.582 g of 50% solution) was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (200.603 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(2.356 g) in 20 ml of water. Then was added silica gel (625 g 40% Zola SiO2) and the melt of metal nitrates.

Comparative example (with Mn). Using the method described above in Example 1, a catalyst of the formula 50 wt.% Cs0.1K0.1Ce0.75Cr0.3Co4.3Ni4.4Mn0.5Fe2.0Bi0.5Mo14.425O57.775+50 wt.% SiO2prepared from the following list: CsNO3(1.485 g), KNO3(0.77 g), Fe(NO3)3N2O (61.559 g), Ni(NO3)26H2O (97.478 g), With(NO3)26H2O (95.345 g), Mn(NO3)2(13.34 g 51.1% solution), Bi(NO3)35H2O (18.478 d) and (NH4)2CE(NO3)6(62.653 g of 50% solution) was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (200.761 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(2.286 g) in 20 ml of water. Then was added silica gel (625 g 40% Zola SiO2) and the melt of metal nitrates.

Comparative example D (Zn). Using the manual, described above in Example 1, a catalyst of the formula 50 wt.% Cs0.1K0.1Ce0.75Cr0.3Co4.3Ni2.2Zn2.0Fe2.0Bi0.5Mo14.425O57.775+50 wt.% SiO2prepared from the following list: CsNO3(1.55 g), KNO3(0.804 g), Fe(NO3)3N2O (64.244 g), Ni(NO3)26N2O (50.865 g), With(NO3)26N2O (99.503 g), Zn(NO3)26H2O (47.301 g), Bi(NO3)35H2O (19.284 g) and (NH4)2Ce(NO3)6(65.385 g of 50% solution) was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (199.759 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(2.385 g) in 20 ml of water. Then was added silica gel (625 g 40% Zola SiO2) and the melt of metal nitrates.

The test catalysts

All tests were carried out in a fluidized bed reactor with a volume of 40 cm3. Propylene was supplied in the reactor with a rate of 0.06 WWH (i.e. the mass of the propylene/weight of catalyst/h). The pressure in the reactor was maintained at a level of 10 psi. The reaction temperature was 430°C. After the stabilization period ˜20 h samples were taken of the reaction products. The waste products are passed through the bubbler scrubbers with cold HCl solution. The speed of the exhaust flow was measured using a film flowmeter, and the composition of the exhaust gases was determined by the end of the experiment using a gas chromatograph, equipped with a gas analyzer with a separator flows. At the end of the experiment, all of the liquid contents of the scrubber was diluted to approximately 200 g of distilled water. As internal standard used hitch 2-butanone in ˜50 g aliquot of the diluted solution. Samples of 2 μl were analyzed on a GC-chromatograph with a flame ionization detector and a column filled with Carbowax. The number of NH3was determined by titration of the excess of free HCl NaOH solution. The following examples illustrate the present invention.

Table
ExampleThe composition of the active phaseFull CONV. With3=CONV. in ANSat. on AN
1Cs0.1K0.1Ce0.75Cr0.3Co4.3Ni4.4Fe2.0Bi0.5Mo14.425O57.77598.582.683.9
2Cs0.1K0.1Li0.3Ce0.58Cr0.12Co5.3Ni3.1Fe1.8Bi0.62Mo13.744O54.85298.881.982.9
AndCs0.1K0.1Ce0.75Cr0.3Co8.7Fe2.0 Bi0.5Mo14.425O57.77595.880.684.4
InCs0.2Ce0.75Cr0.3Co4.3Ni4.4Fe2.0Bi0.5Mo14.425O57.77596.680.583.3
Cs0.1K0.1Ce0.75Cr0.3Co4.3Ni4.4Mn0.5Fe2.0Bi0.5Mo14.425O57.77599.481.682.0
DCs0.1K0.1Ce0.75Cr0.3Co4.3Ni2.2Zn2.0Fe2.0Bi0.5Mo14.425O57.77596.481.084.0
Notes.
1. All tested catalysts contained 50% of the active phase and 50% SiO2.
2. "Total conversion With3=" means molar conversion of propylene (in percent) all products in a single pass per missed propylene.
3. "CONV. in AN" means molar conversion of propylene (%) Acrylonitrile in a single pass.
4. "Villages. on AN" is the ratio of the number of moles of the resulting Acrylonitrile to the number of moles converted propylene, expressed as a percentage.

Example 3. Using methods prepara is to be placed, similar to the methods described above in Example 2, there were prepared several catalysts (50% of the active phase and 50% SiO2)containing lithium. The active phase had the following composition:

Cs0.1K0.1Li0.3Ce1.0Cr0.12Co5.3Ni3.1Fe1.8Bi0.62Mo14.44O57.78

Cs0.1K0.1Li0.3Ce0.8Cr0.12Co5.3Ni3.1Fe1.8Bi0.62Mo14.074O56.282

Cs0.1K0.1Li0.3Ce0.8Cr0.12Co4.2Ni4.2Fe1.8Bi0.62Mo14.074O56.282

Cs0.1K0.1Li0.3Ce1.0Cr0.12Co1.0Ni7.4Fe1.8Bi0.62Mo14.374O57.532

Cs0.1K0.1Li0.3Ce1.0Cr0.12Co5.3Ni3.1Fe1.8Bi0.62Mo14.074O57.582

Cs0.1K0.1Li0.3Ce0.8Cr0.5Co5.3Ni3.1Fe1.8Bi0.62Mo13.969O55.862

Cs0.1K0.1Li0.3Na0.2Ce1.0Cr0.12Co1.0Ni7.4Fe1.8Bi0.62Mo14.374O57.982

Cs0.1K0.1Li0.1Ce1.0Cr0.12Co4.2Ni4.2Fe1.8Bi0.62Mo14.26O57.14

Cs0.1K0.1Li0.3Ce1.0Cr0.12Co4.2Ni4.2Fe1.8Bi0.62Mo14.16O56.94

Cs0.1K0.1Li0.3Na0.2Ce0.8Cr0.12Co4.2Ni4.2 Fe1.8Bi0.62Mo14.16O56.64

Cs0.1K0.1Li0.1Ce1.0Cr0.12Co2.0Ni5.0Fe1.8Bi0.62Mo12.86O51.54

Cs0.1K0.1Li0.1Ce1.0Cr0.12Co3.2Ni4.2Fe2.0Bi0.62Mo14.26O54.04

Cs0.1K0.1Li0.1Na0.2Ce1.0Cr0.12Co4.2Ni4.2Fe1.8Bi0.62Mo14.36O57.54

Cs0.1K0.1Li0.3Ce0.8Cr0.12Co4.2Ni4.2Fe2.2Bi0.62Mo14.76O59.34

The above compounds were tested as described above. Complete conversion to nitrile (i.e. molar percent conversion to Acrylonitrile, acetonitrile and hydrogen cyanide) missed propylene for these catalysts ranged from about 86% to about 88%.

The composition of the catalyst according to the present invention is unique in that it contains potassium, cesium, chromium, cobalt, Nickel, iron, bismuth and molybdenum in the absence of significant amounts of manganese and zinc. This combination of elements in the relative proportions shown in the invention, not previously used in any catalyst of oxidative ammonolysis. As shown in table 1, in the reaction of oxidative ammonolysis of propylene to Acrylonitrile catalyst according to the present invention exhibits a higher activity than the ka is aleatory with similar (but not exactly) combinations of elements, proposed in prior patents. More specifically, a catalyst containing potassium, cesium, chromium, cobalt, Nickel, iron, bismuth and molybdenum in the absence of manganese or zinc, showed a higher complete conversion and a higher conversion to Acrylonitrile in the oxidative ammonolysis of propylene in the presence of the specified catalyst at elevated temperatures and in the presence of ammonia and air compared with similar catalysts, remaining outside the scope of the present invention.

Although the above description of a typical embodiment for practice of the present invention, it is obvious that the experts in this field will be able to offer various alternatives, modifications and variations. Accordingly, it is assumed that all these alternatives, modifications and variations will be within the scope of the claims.

1. The composition of the catalyst for the ammonolysis of the unsaturated hydrocarbon to an unsaturated nitrile, which is a complex catalytically active oxides, including oxides of potassium, cesium, cerium, chromium, cobalt, Nickel, iron, bismuth and molybdenum, in which the relationships of the elements represented by the following General formula:

AaKbCscCedCreCofNigFeiBijMo12Ox,

in which a represents a Rb, Li, or a mixture thereof,

a is from 0 to 1,

b is equal to from 0.01 to 1,

with equal to from 0.01 to 1,

d is equal to from 0.01 to 3,

e is equal to from 0.01 to 2,

f is equal to from 0.01 to 10,

g is equal to from 0.1 to 10,

i equal to from 0.1 to 4,

j is equal to from 0.05 to 4,

x is a number determined by the valence requirements of the other elements present, and the catalyst contains manganese and zinc and supported on a carrier selected from the group consisting of silica gel, aluminum oxide, zirconium oxide, titanium oxide or mixtures thereof.

2. The catalyst composition according to claim 1, characterized in that a represents a RB.

3. The catalyst composition according to claim 1, characterized in that a represents lithium.

4. The catalyst composition according to claim 1, characterized in that f+g is from 4 to 10.

5. The catalyst composition according to claim 1, characterized in that the carrier is 30 to 70 wt.% catalytic Converter.

6. The catalyst composition according to claim 1, characterized in that the carrier is a silica gel with an average size of colloidal particles is from 8 to 100 nm.

7. The composition of the catalyst for the ammonolysis of the unsaturated hydrocarbon to an unsaturated nitrile, which is a complex catalytically active oxides, including oxides of potassium, cesium, cerium, chromium, cobalt, Nickel, iron, bismuth and molybdenum, in which the ratio of the elements presented following the th General formula:

AaLia'KbCscCedCreCofNigFeiBijMo12Ox,

in which a represents a Rb,

a is from 0 to 1,

and' equal to from 0.01 to 1,

b is equal to from 0.01 to 1,

with equal to from 0.01 to 1,

d is equal to from 0.01 to 3,

e is equal to from 0.01 to 2,

f is equal to from 0.01 to 10,

g is equal to from 0.1 to 10,

i equal to from 0.1 to 4,

j is equal to from 0.05 to 4,

x is a number determined by the valence requirements of the other elements present,

moreover, the catalyst does not contain manganese and zinc and supported on a carrier selected from the group consisting of silica gel, aluminum oxide, zirconium oxide, titanium oxide or mixtures thereof.

8. The catalyst composition according to claim 7, characterized in that f+g is from 4 to 10.

9. The method of conversion of the olefin selected from the group consisting of propylene, isobutylene or mixtures thereof, to Acrylonitrile, Methacrylonitrile and mixtures thereof, respectively, by reaction in the vapor phase specified olefin with a gas containing molecular oxygen and ammonia in the presence of a catalyst comprising a catalytically active complex oxides, including oxides of potassium, cesium, cerium, chromium, cobalt, Nickel, iron, bismuth, molybdenum, in which the relationships of the elements represented by the following General formula:

AaKbCscCedCreCofNigFeiBijMo12Ox,

in which a represents a Rb, Li, or a mixture thereof,

a is from 0 to 1,

b is equal to from 0.01 to 1,

with equal to from 0.01 to 1,

d is equal to from 0.01 to 3,

e is equal to from 0.01 to 2,

f is equal to from 0.01 to 10,

g is equal to from 0.1 to 10,

i equal to from 0.1 to 4,

j is equal to from 0.05 to 4,

x is a number determined by the valence requirements of the other elements present,

moreover, the catalyst does not contain significant amounts of manganese and zinc and supported on a carrier selected from the group consisting of silica gel, aluminum oxide, zirconium oxide, titanium oxide or mixtures thereof.

10. The method according to claim 9, characterized in that a represents a RB.

11. The method according to claim 9, characterized in that a represents lithium.

12. The method according to claim 9, characterized in that f+g is from 4 to 10.

13. The method according to claim 9, characterized in that the carrier is 30 to 70 wt.% catalytic Converter.

14. The method according to claim 9, characterized in that the carrier is a silica gel with an average size of colloidal particles is from 8 to 100 nm.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: present invention pertains to perfection of the method of obtaining at least, one product of partial oxidation and/or ammoxidising of propylene, chosen from a group, comprising propylene oxide, acrolein, acrylic acid and acrylonitrile. The starting material is raw propane. a) At the first stage, raw propane, in the presence and/or absence of oxygen, is subjected to homogenous and/or heterogeneous catalysed dehydrogenation and/or oxydehydrogenation. Gas mixture 1, containing propane and propylene is obtained. b) If necessary, a certain quantity of the other components in gas mixture 1, obtained in the first stage, besides propane and propylene, such as hydrogen and carbon monoxide is separated and/or converted to other compounds, such as water and carbon dioxide. From gas mixture 1, gas mixture 1' is obtained, containing propane and propylene, as well as other compounds, besides oxygen, propane and propylene. c) At the third stage, gas mixture 1 and/or gas mixture 1' as a component, containing molecular oxygen, of gas mixture 2, is subjected to heterogeneous catalysed partial gas-phase oxidation and/or propylene, contained in gas mixture 1 and/or gas mixture 1', undergoes partial gas-phase ammoxidising. Content of butane-1 in gas mixture 2 is ≤1 vol.%. The method increases output of desired products and efficiency of the process.

EFFECT: increased output of desired products and efficiency of the process.

72 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: proposed catalyst contains a complex of catalytically active oxides, including oxides of rubidium, cerium, chrome, magnesium, iron, bismuth, molylbdenum and at least, one of nickel or nickel with cobalt. The ratio of components is presented by the following general formula: RbaCebCrcMgdAeFefBigMo12Ox, where A is Ni or a combination of Ni and Co, a approximately ranges from 0.01 to 1, b approximately ranges from 0.01 to 3, c approximately ranges from 0.01 to 2, d approximately ranges from 0.01 to 7, e approximately ranges from 0.01 to 10, f approximately ranges from 0.01 to 4, g approximately ranges from 0.01 to 4, and x is a number, defined by valency of other present elements. "b"+"c" is greater than g. The catalyst does not contain manganese, noble metal or vanadium. The carrier is chosen from a group comprising silica gel, aluminium oxide, zirconium oxide, titanium oxide or their mixture. The catalyst is used for oxidative ammonolysis of olefin, chosen from a group containing isobutylene or their mixture, with formation of acrylonitrile, metacrylontrile and their mixture, respectively.

EFFECT: high activity of the catalyst.

19 cl, 1 tbl, 16 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

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for reducing breakthrough fraction of ammonia in the process for manufacturing acrylonitrile. Method involves addition of hydrocarbon taken among the group consisting of propane and isobutene, ammonium and oxygen-containing gas to the bottom reactor compartment with fluidized bed and containing a catalyst for ammoxidation followed by interaction in the presence of indicated catalyst to form acrylonitrile. Method involves addition into reactor in the point lower by flow from feeding alkane of at least one among from C2- to C5-olefins that reacts with at least part of unreacted ammonia and oxygen presenting in the reactor that allows to carry out the significant reducing the ammonia amount presenting in the reaction flow coming out from the reactor. Except for, invention relates to a method for conversion of acrylonitrile manufacture based on propylene raw wherein propylene, ammonia and oxygen react in reactor in the presence the catalyst used in acrylonitrile manufacturing to the process of acrylonitrile manufacturing based on propane raw wherein propane, ammonia and oxygen reacts in the presence of catalyst used in preparing acrylonitrile. Method involves the following stages: (a) replacing the parent propylene-base raw with the propane-base parent raw; (b) addition into reactor in the point lower by flow from feeding alkane of at least one among from C2- to C5-olefin that reacts with at least part of unreacted ammonia and oxygen presenting in the reactor that results to reducing the amount of ammonia presenting in the reaction flow coming out from the reactor, and (c) addition agents for separation, trapping and recycling of unreacted propane to the process.

EFFECT: improved manufacturing method.

13 cl, 19 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to methods (variants) for producing acrylonitrile and preparing hydrogen cyanide and acetonitrile as co-products. Methods involve addition of hydrocarbon that is taken among propylene or propane, ammonia and oxygen-containing gas to the reaction zone containing a catalyst for oxidative ammonolysis and reaction is carried out at increased temperature to form acrylonitrile, hydrogen cyanide and acetonitrile, and isolation of acrylonitrile, hydrogen cyanide and acetonitrile from reactor also. According to the first variant reaction is carried out in the presence of alcohols mixture containing methanol and a second alcohol among ethanol, propanol or their mixtures wherein the weight ratio of methanol to the second alcohol in alcohols mixture is maintained depending on necessary amounts of hydrogen cyanide and acetonitrile. According to the second variant reaction is carried out in the presence of alcohols mixture containing methanol and ethanol taken in the weight ratio from about 99:1 to 1::99. According to the third variant reaction is carried out in the presence of one or more alcohols taken among crude methanol, crude ethanol or crude propanol. According to the fourth variant reaction is carried out in the presence of one or more crude (C1-C4)-alcohol. Proposed method provides enhancing yield of one or both co-products, i. e. HCN and acetonitrile, formed in producing acrylonitrile.

EFFECT: improved producing method.

21 cl, 2 tbl, 8 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for extraction of acrylonitrile, methacrylonitrile or hydrogen cyanide obtained from the reaction flow in the ammoxidation reaction of propane, propylene or isobutylene that involves passing the reactor flow through absorption column, extraction column and head fraction column. Method involves using such regimen of the process to prevent formation of an aqueous phase above feeding plate in the head fraction column. Method provides reducing unfavorable polymerization of hydrogen cyanide that provides significant decreasing or excluding stoppage of the head fraction column.

EFFECT: improved method for extraction.

12 cl, 1 dwg, 7 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for extraction of organic material comprising hydrogen cyanide prepared in reactor flow in carrying out the ammoxidation reaction of propylene or isobutylene for preparing acrylonitrile or methacrylonitrile followed by feeding vapor flows from technological devices to the torch head part. At least one part of organic material from torch head part comprising hydrogen cyanide is fed to the extraction stage. Method provides reducing amount of acrylonitile and HCN feeding to combustion.

EFFECT: improved method for extraction.

9 cl

FIELD: industrial organic synthesis.

SUBSTANCE: process, in which, in particular, acrylonitrile or methacrylonitrile are obtained, comprises reacting hydrocarbon selected from propane, propylene, and isobutylene with ammonia and oxygen source in presence of catalyst in reaction zone at elevated temperature. Reactor effluent containing unsaturated mononitrile is transferred into first column to be cooled therein with the aid of the first water stream. Cooled effluent containing unsaturated mononitrile is transferred into second column wherein it comes into contact with second water stream to absorb unsaturated mononitrile. Unsaturated mononitrile-containing second column effluent is fed into first distillation column to separate crude unsaturated mononitrile from the second water stream and routed to the second distillation column to remove at least some impurities from crude mononitrile, which is transferred into third distillation column to be further purified. Water in the form of steam and/or distilled water is added in amounts 100 to 2000 ppm to side-cut distillate containing purified mononitrile or to bottom stream coming out of the third distillation column. At least part of the latter is recycled into lower section of third distillation column or directly into column below side-cut distillate withdrawal point.

EFFECT: enhanced process efficiency.

16 cl, 1 dwg

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

FIELD: chemistry.

SUBSTANCE: present invention pertains to perfection of the method of obtaining at least, one product of partial oxidation and/or ammoxidising of propylene, chosen from a group, comprising propylene oxide, acrolein, acrylic acid and acrylonitrile. The starting material is raw propane. a) At the first stage, raw propane, in the presence and/or absence of oxygen, is subjected to homogenous and/or heterogeneous catalysed dehydrogenation and/or oxydehydrogenation. Gas mixture 1, containing propane and propylene is obtained. b) If necessary, a certain quantity of the other components in gas mixture 1, obtained in the first stage, besides propane and propylene, such as hydrogen and carbon monoxide is separated and/or converted to other compounds, such as water and carbon dioxide. From gas mixture 1, gas mixture 1' is obtained, containing propane and propylene, as well as other compounds, besides oxygen, propane and propylene. c) At the third stage, gas mixture 1 and/or gas mixture 1' as a component, containing molecular oxygen, of gas mixture 2, is subjected to heterogeneous catalysed partial gas-phase oxidation and/or propylene, contained in gas mixture 1 and/or gas mixture 1', undergoes partial gas-phase ammoxidising. Content of butane-1 in gas mixture 2 is ≤1 vol.%. The method increases output of desired products and efficiency of the process.

EFFECT: increased output of desired products and efficiency of the process.

72 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: proposed catalyst contains a complex of catalytically active oxides, including oxides of rubidium, cerium, chrome, magnesium, iron, bismuth, molylbdenum and at least, one of nickel or nickel with cobalt. The ratio of components is presented by the following general formula: RbaCebCrcMgdAeFefBigMo12Ox, where A is Ni or a combination of Ni and Co, a approximately ranges from 0.01 to 1, b approximately ranges from 0.01 to 3, c approximately ranges from 0.01 to 2, d approximately ranges from 0.01 to 7, e approximately ranges from 0.01 to 10, f approximately ranges from 0.01 to 4, g approximately ranges from 0.01 to 4, and x is a number, defined by valency of other present elements. "b"+"c" is greater than g. The catalyst does not contain manganese, noble metal or vanadium. The carrier is chosen from a group comprising silica gel, aluminium oxide, zirconium oxide, titanium oxide or their mixture. The catalyst is used for oxidative ammonolysis of olefin, chosen from a group containing isobutylene or their mixture, with formation of acrylonitrile, metacrylontrile and their mixture, respectively.

EFFECT: high activity of the catalyst.

19 cl, 1 tbl, 16 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention is dealing with catalyst applicable in saturated hydrocarbon ammoxidation process resulting in corresponding unsaturated nitrile. Catalyst composition of invention comprises complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of nickel and magnesium, and at least one of lithium, sodium, potassium, rubidium, and thallium and is described by following empirical formula: AaBbCcFedBieCofCegSbhMomOx, wherein A represents at least one of Cr, P, Sn, Te, B, Ge, Zn, In, Mn, Ca, W, and mixtures thereof; B represents at least one of Li, Na, K, Rb, Cs, Ti, and mixtures thereof; C represents at least one of Ni, Mg, and mixtures thereof; a varies from 0 to 4.0, b from 0.01 to 1.5, c from 1.0 to 10.0, d from 0.1 to 5.0, e from 0.1 to 2.0, f from 0.1 to 10.0, g from 0.1 to 2.0, h from 0.1 to 2.0, m from 12.0 to 18.0, and m is a number determined by requirements of valences of other elements present. Ammoxidation processes for propylene, ethylene, or their mixtures to produce, respectively, acrylonitrile, methacrylonitrile, or their mixtures in presence of above-defined catalytic composition is likewise described.

EFFECT: increased olefin conversion.

9 cl, 1 tbl

FIELD: chemical technology.

SUBSTANCE: invention relates to a method for reducing breakthrough fraction of ammonia in the process for manufacturing acrylonitrile. Method involves addition of hydrocarbon taken among the group consisting of propane and isobutene, ammonium and oxygen-containing gas to the bottom reactor compartment with fluidized bed and containing a catalyst for ammoxidation followed by interaction in the presence of indicated catalyst to form acrylonitrile. Method involves addition into reactor in the point lower by flow from feeding alkane of at least one among from C2- to C5-olefins that reacts with at least part of unreacted ammonia and oxygen presenting in the reactor that allows to carry out the significant reducing the ammonia amount presenting in the reaction flow coming out from the reactor. Except for, invention relates to a method for conversion of acrylonitrile manufacture based on propylene raw wherein propylene, ammonia and oxygen react in reactor in the presence the catalyst used in acrylonitrile manufacturing to the process of acrylonitrile manufacturing based on propane raw wherein propane, ammonia and oxygen reacts in the presence of catalyst used in preparing acrylonitrile. Method involves the following stages: (a) replacing the parent propylene-base raw with the propane-base parent raw; (b) addition into reactor in the point lower by flow from feeding alkane of at least one among from C2- to C5-olefin that reacts with at least part of unreacted ammonia and oxygen presenting in the reactor that results to reducing the amount of ammonia presenting in the reaction flow coming out from the reactor, and (c) addition agents for separation, trapping and recycling of unreacted propane to the process.

EFFECT: improved manufacturing method.

13 cl, 19 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to methods (variants) for producing acrylonitrile and preparing hydrogen cyanide and acetonitrile as co-products. Methods involve addition of hydrocarbon that is taken among propylene or propane, ammonia and oxygen-containing gas to the reaction zone containing a catalyst for oxidative ammonolysis and reaction is carried out at increased temperature to form acrylonitrile, hydrogen cyanide and acetonitrile, and isolation of acrylonitrile, hydrogen cyanide and acetonitrile from reactor also. According to the first variant reaction is carried out in the presence of alcohols mixture containing methanol and a second alcohol among ethanol, propanol or their mixtures wherein the weight ratio of methanol to the second alcohol in alcohols mixture is maintained depending on necessary amounts of hydrogen cyanide and acetonitrile. According to the second variant reaction is carried out in the presence of alcohols mixture containing methanol and ethanol taken in the weight ratio from about 99:1 to 1::99. According to the third variant reaction is carried out in the presence of one or more alcohols taken among crude methanol, crude ethanol or crude propanol. According to the fourth variant reaction is carried out in the presence of one or more crude (C1-C4)-alcohol. Proposed method provides enhancing yield of one or both co-products, i. e. HCN and acetonitrile, formed in producing acrylonitrile.

EFFECT: improved producing method.

21 cl, 2 tbl, 8 ex

FIELD: industrial organic synthesis.

SUBSTANCE: process, in which, in particular, acrylonitrile or methacrylonitrile are obtained, comprises reacting hydrocarbon selected from propane, propylene, and isobutylene with ammonia and oxygen source in presence of catalyst in reaction zone at elevated temperature. Reactor effluent containing unsaturated mononitrile is transferred into first column to be cooled therein with the aid of the first water stream. Cooled effluent containing unsaturated mononitrile is transferred into second column wherein it comes into contact with second water stream to absorb unsaturated mononitrile. Unsaturated mononitrile-containing second column effluent is fed into first distillation column to separate crude unsaturated mononitrile from the second water stream and routed to the second distillation column to remove at least some impurities from crude mononitrile, which is transferred into third distillation column to be further purified. Water in the form of steam and/or distilled water is added in amounts 100 to 2000 ppm to side-cut distillate containing purified mononitrile or to bottom stream coming out of the third distillation column. At least part of the latter is recycled into lower section of third distillation column or directly into column below side-cut distillate withdrawal point.

EFFECT: enhanced process efficiency.

16 cl, 1 dwg

The invention relates to catalysts for the selective decomposition of N2About in a mixture of nitrous gases

The invention relates to a method for producing a catalyst for the (AMM)oxidation of propane or propylene to Acrylonitrile

FIELD: chemistry.

SUBSTANCE: invention concerns neutralisation catalysts for exhaust gas (EG) of internal combustion engines (ICE) and industrial effluent gas. Catalyst is obtained due to: 1) adding orthophosphoric acid to coating suspension to obtain alumophosphate, a binding substance, the total composition of which serves for coating reinforcement and thermal stabilisation of porous coating structure; 2) energy heterogeneity increase by adding zyrconyl dihydrophosphate to coating suspension, so that the total composition serves to enhance heat resistance of both modified aluminium oxide and catalytic contacts, i.e. of the whole catalyst. Invention claims method of catalyst preparation, involving preliminary processing of inert Al-containing foil block carrier by baking at 850-920°C in air flow for 12-15 hours, followed by carrier application onto intermediary modified aluminium oxide coating surface from suspension at room temperature, thermal processing of block with intermediary coating in air flow and further applying one or more active catalytic metals of platinum group. Intermediary coating is applied from suspension containing additionally orthophosphoric acid and zyrconyl dihydrophosphate at the following component ratio, wt %: aluminium hydroxide (pseudobemite) - 22-32, aluminium nitrite - 2-4, cerium nitrite - 2-5, orthophosphoric acid - 1-2, zyrconyl dihydrophosphate - 1-3, water - up to 100; thermal processing of block with intermediary coating is performed at 620-650°C with maturing for 1.8-2 hours. Invention also claims catalyst including metal block carrier, intermediary coating of modified aluminium oxide and active phase of noble metals of platinum group applied onto porous surface of intermediary coating. Catalyst includes 7-14 wt % of modified Al2O3 with specific surface area of 120-130 m2/g, which includes additionally aluminium phosphate and zyrconyl phosphate at the following weight ratio of coating components (%): aluminium oxide (89.7-71.4), cerium oxide - (3.5-9.7), aluminium phosphate - (3.6-8.1), zyrconyl dihydrophosphate - (3.2-10.9).

EFFECT: significant enhancement of mechanical and heat resistance of catalytic coating at high efficiency in waste gas treatment process, prolonged lifetime.

2 cl, 2 tbl, 26 ex

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