Catalyst for production of acrylonitrile

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

 

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 the catalytically active complex oxides of iron, bismuth, molybdenum, magnesium and at least one element of Nickel or Nickel and cobalt, rubidium, cerium and chromium in the practical absence of manganese, a noble metal and vanadium.

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 Vism the t-molybdenum-iron catalyst for the oxidation of olefins. U.S. patent No. 5093299, 5212137, 5658842 and 5834394 dedicated bismuth-molybdenum catalysts receipt of Acrylonitrile with large outputs.

The aim of the present invention is a new 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 relates 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 rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and at least one of the metals Nickel or Nickel and cobalt, in which the ratio of these elements is represented by the following General formula:

RbaCebCrcMgdAeFefBigMo12Ox

where And represents Ni or the combination of Ni and Co,

and equal to from about 0.01 to about 1,

b is equal to from about 0.01 to about 3,

equals from about 0.01 to about 2,

d is equal to from about 0.01 to about 7,

e equals approx the RNO 0.01 to about 10,

f is equal to from about 0.01 to about 4,

g is equal to from about 0.01 to about 4,

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

and b + C is greater than g, and the catalyst does not contain significant amounts of manganese, precious metal or vanadium.

In the second embodiment of the invention the catalyst is a catalytically active complex oxides, including oxides of rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and at least one of the metals Nickel or Nickel and cobalt, and optionally one of the elements phosphorus, antimony, tellurium, sodium, lithium, potassium, cesium, thallium, boron, tungsten, calcium, in which the ratio of the elements represented by the following General formula:

RbaCebCrcMgdAeFefBigYhMo12Ox

where And represents Ni or the combination of Ni and Co,

Y represents at least one element of P, Sb, Te, Li, Na, K, Cs, Tl, In, Ge, W, Ca, Zn, and rare earth element or mixtures thereof,

and equal to from about 0.01 to about 1,

b is equal to from about 0.01 to about 3,

equals from about 0.01 to about 2,

d is equal to from about 0.01 to about 7,

e is equal to from about 0.01 to about 10,

f is equal to from about 0.01 to about 4,

g is equal to from about 0.01 to about 4,

h is equal to from 0 to about 3,

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

and b + C is greater than g, and the catalyst does not contain significant amounts of manganese, precious metal or vanadium.

In the third embodiment of the invention the catalyst is a catalytically active complex oxides, including oxides of rubidium, cerium, chromium, iron, bismuth, molybdenum and at least one of the metals Nickel or Nickel and cobalt, and optionally one of the elements phosphorus, antimony, tellurium, sodium, lithium, potassium, cesium, thallium, boron, tungsten, calcium, in which the relationships of the elements represented by the following General formula:

RbaCebCrcAeFefBigYhMo12Ox

where And represents Ni or the combination of Ni and Co,

Y represents at least one element of P, Sb, Te, Na, Li, K, Cs, Tl, In, Ge, W, Ca, Zn, and rare earth element or mixtures thereof,

and equal to from about 0.01 to about 1,

b is equal to from about 0.01 to about 3,

equals from about 0.01 to about 2,

e is equal to from about 0.01 to about 10,

f is equal to from about 0.01 to about 4,

g is equal to from about 0.05 to about 4,

h is equal to from 0 to about 3,

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

PR is less than b + more than g, and the catalyst does not contain significant amounts of manganese, precious metal or vanadium.

The present invention also provides methods 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, and the catalyst described above.

Detailed description of the invention

A new catalyst, which 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.

One embodiment of the present invention is devoted to the catalyst of oxidative ammonolysis of representing complex catalytically active oxides, including oxides of rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and at least one of the metals Nickel or Nickel and cobalt, in which the ratio of the elements represented by the following General formula:

RbaCebCrcMgdAeFefBigMo12 Ox

where And represents Ni or the combination of Ni and Co,

and equal to from about 0.01 to about 1,

b is equal to from about 0.01 to about 3,

equals from about 0.01 to about 2,

d is equal to from about 0.01 to about 7,

e is equal to from about 0.01 to about 10,

f is equal to from about 0.01 to about 4,

g is equal to from about 0.05 to about 4,

h is equal to from 0 to about 3,

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

and b + C is greater than g, and the catalyst does not contain significant amounts of manganese, precious metal or vanadium. In another embodiment b is greater than C. In yet another embodiment of the present invention is from 0.05 to 0.3.

In yet another embodiment of the present invention is devoted to the catalyst of oxidative ammonolysis, which is a complex catalytically active oxides, including oxides of rubidium, cerium, chromium, iron, bismuth, molybdenum and at least one of the metals Nickel or Nickel and cobalt, and optionally one of the elements phosphorus, antimony, tellurium, sodium, lithium, potassium, cesium, thallium, boron, germanium, tungsten and calcium, in which the relationships of the elements represented by the following General formula:

RbaCebCrcMgdAeFefBigYhMo12Ox

who And which represents Ni or the combination of Ni and Co,

Y represents at least one element of P, Sb, Te, Na, Li, K, Cs, Tl, In, Ge, W, Ca, Zn, and rare earth element or mixtures thereof,

and equal to from about 0.01 to about 1,

b is equal to from about 0.01 to about 3,

equals from about 0.01 to about 2,

d is equal to from 0 to about 7, preferably d is equal to from 0.01 to about 7,

e is equal to from about 0.01 to about 10,

f is equal to from about 0.01 to about 4,

g is equal to from about 0.05 to about 4,

h is equal to from 0 to about 3,

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

and b + C is greater than g, and the catalyst does not contain significant amounts of manganese, precious metal or vanadium. In another embodiment b is greater than C. In yet another embodiment of the present invention is from 0.05 to 0.3.

In the above compositions of the catalysts atomic number of cerium plus chromium greater than the atomic number of bismuth (i.e. b + C is greater than g). If the atomic number of cerium plus chromium is less than the number of bismuth, the catalysts are not active. In another embodiment, the atomic number of pulses is greater than the number of chromium (i.e. b is greater than C).

The basic composition of the catalyst described in the invention is a complex catalytically active oxides of rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and what about the at least one of the metals Nickel or Nickel and cobalt. Except as specifically excluded items may have other elements or promoters. In one embodiment the catalyst may contain one or more of the elements phosphorus, antimony, tellurium, sodium, lithium, potassium, cesium, thallium, boron, germanium, tungsten, calcium, zinc and rare earth element (denoted in the text as one element of La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb). In another embodiment, the base catalyst may not contain magnesium. In yet another embodiment the catalyst contains a small amount of phosphorus, which has a positive effect on the stability of the catalyst to abrasion.

In addition, it was shown that the introduction of some elements is not possible to obtain higher outputs of Acrylonitrile by the reaction of conversion of propylene, ammonia and oxygen. These elements include manganese, noble metals used in the invention, the term "noble metals" refers to ruthenium, rhodium, palladium, osmium, iridium and platinum and vanadium. The introduction of the noble metal in the catalyst promotiom oxidation of ammonia and thereby reduce the amount of ammonia available for the formation of Acrylonitrile. The introduction of vanadium results in a catalyst which is more active in the reaction of propylene and less selective in the formation of the target product, in accordance with the ATA, which produces more carbon oxides (CO xand less of Acrylonitrile. The introduction of manganese in the catalyst leads to a reduction of yield of Acrylonitrile. Therefore, the catalyst of the present invention is referred to as not containing significant quantities of manganese, precious metal and/or vanadium. Used the term "does not contain significant amounts" with respect to manganese and vanadium means that the atomic ratio of the metal molybdenum is less than 0.2:12. With respect to the noble metal, the term refers to the atomic ratio of metal/molybdenum 0.005:12. Preferably, the catalyst did not contain manganese, precious metals and/or vanadium.

The catalyst according to the present invention can be used as applied or not applied (i.e., the catalyst may contain a carrier). Suitable carriers are the oxides of silicon, aluminum, zirconium, titanium or mixtures thereof. Typically, the media serves as a binder 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 energy is 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. The media may contain one or more of the promoting elements, such as silica Sol containing sodium (Na), and these promoters can be introduced into the catalyst through the media.

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 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 among the deposits of the diameter of colloidal particles or Sol of silica is approximately 20 nm.

The catalysts of the present invention can be obtained in 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 the mass is dried and milled 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 methods 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. Particularly preferred source for the introduction of 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 is Olya, 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 in any form of molybdenum oxide. 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 in any appropriate 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 turn into the oxide. Phosphorus can be introduced into the catalyst in the form of a salt of an alkali metal 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, Cs, Tl or a mixture thereof) can be introduced into the catalyst in the form of the oxide or salt, which upon annealing into the oxide. It is preferable to introduce these elements in the catalyst to use salt such as nitrate, which is easily accessible.

Usually kata is history 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 to 350°C, preferably from 110 to 250°S, most preferably from 110 to 180°C. Temperature denitrification may be in the range from 100 to 500°C, preferably from 250 to 450°C. Finally, annealing is conducted at a temperature of from 300 to 700°C, preferably from 350 to 650°C.

The catalysts of the present invention is used 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 in the fluidized bed reactor, 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 of the well and the known, as it follows from the U.S. patent No. 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 may be in the range of from 0.5:1 to 2:1. Generally the upper limit for the ammonia/olefin does not exist, but in principle 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 of ammonia to propylene from 0.9:1 to 1.3:1 and the relationship of air to 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 helped the Ute to reduce the amount of unreacted ammonia in the exhaust gas reactor 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 to 500°S, particularly preferably from 350 to 480°C. the contact Time, although not critical, is in the range from 0.1 to 50 seconds, the preferred contact time is from 1 to 15 seconds.

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 of the reactor through a 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 what to use for the oxidation of propylene to acrylic acid. Such processes are typically two-stage: in the first stage, propylene is 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. The proposed 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 of 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.% Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15Mo12O45.4+50 wt.% SiO2was prepared as follows. The nitrates of the metals were fused in the following order: Fe(NO3)39H2O (69.752 g), Ni(NO3)26N2O (139.458 g), Mg(NO3)26H2O (49.186 g), Bi(NO3)35H2O (20.937 g), RbNO3(2.122 g) and (NH4)2CE(NO3)6(94.654 g of 50% solution) at ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (203.219 g) was dissolved in 310 m is distilled water. To this solution was added a solution of CrO3(0.959 g) in 20 ml of water. Then was added silica gel (871.08 g 28.75% 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:

50 wt.% Ni2.5Mg2.0Co2.5Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15Mo12O48.4+50 wt.% SiO2

This catalyst was prepared as described in example 1. The set of components was as follows: Fe(NO3)3N2On (69.737 g), Ni(NO3)26N2O (69.714 g), Mg(NO3)26N2O (49.176 g), With(NO3)26N2O (69.774 g), Bi(NO3)35H2O (20.993 g), RbNO3(2.121 g) and (NH4)2CE(NO3)6(94.63 g of 50% solution), was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (203.175 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(0.959 g) in 20 ml of water. Then was added silica gel (796.178 g 31.4% Zola SiO2) and the melt of metal nitrates.

Example 3:

50 wt.% Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Li0.3Rb0.15Mo12O48.55+50 wt.% SiO2

This catalyst was prepared as described in example 1. The feature set was the following is relevant: Fe(NO 3)3N2O (69.632 g), Ni(NO3)26N2O (139.219 g), Mg(NO3)26H2O (49.102 g), LiNO3(1.981 g), Bi(NO3)35H2O (20.901 g), RbNO3(2.118 g) and (NH4)2CE(NO3)6(94.634 g of 50% solution), was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (202.87 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(0.958 g) in 20 ml of water. Then was added silica gel (796.178 g 31.4% Zola SiO2) and the melt of metal nitrates.

Example 4:

50 wt.% Ni2.5Mg2.0Co2.5Fe1.8Bi0.45Ce0.9Cr0.1P0.1Rb0.15Mo12O48.95+50 wt.% SiO2

This catalyst was prepared as described in example 1. The set of components was as follows: Fe(NO3)3N2O (68.936 g), Ni(NO3)26N2On (68.914 g), Mg(NO3) 6N2On (48.61 g), With(NO3)26N2On (68.973 g), Bi(NO3)35H2O (20.693 g), RbNO3(2.097 g) and (NH4)2CE(NO3)6(93.547 g of 50% solution), was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (200.842 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of N3PO4(1.093 g 85% solution), (NH4)6H2W12O40(2.388 g) and CrO3(0.948 g) in 20 ml of water. Then was added silica gel (796.178 g 31.4% Zola SiOsub> 2) and the melt of metal nitrates.

Example 5:

50 wt.% Ni5.0Mg2.0Co2.5Fe1.8Bi0.45Ce0.9Cr0.1Na0.2Rb0.15Mo12O48.5+50 wt.% SiO2

This catalyst was prepared as described in example 1. The set of components was as follows: Fe(NO3)3N2O (69.586 g), Ni(NO3)26N2O (139.127 g), Mg(NO3)26N2O (49.07. g), NaNO3(1.626 g), Bi(NO3)35H2O (20.888 g), RbNO3(2.117 d) and (NH4)2CE(NO3)6(94.429 g of 50% solution), was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (202.736 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(0.957 g) in 20 ml of water. Then was added silica gel (796.178 g 31.4% Zola SiO2) and the melt of metal nitrates.

Example 6:

50 wt.% Ni5.0Mg2.0Co2.5Fe1.8Bi0.45Ce0.9Cr0.1P0.1Rb0.15Mo12O48.65+50 wt.% SiO2

This catalyst was prepared as described in example 1. The set of components was as follows: Fe(NO3)3N2O (69.562 g), Ni(NO3)26N2O (139.079 g), Mg(NO3)26N2O (49.053 g), Bi(NO3)35H2O (20.881 g), RbNO3(2.097 g) and (NH4)2CE(NO3)6(94.397 g of 50% solution), was fused at -70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN)(202.667 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of N3PO4(1.103 g 85% solution) and CrO3(0.957 g) in 20 ml of water. Then was added silica gel (796.178 g 31.4% Zola SiO2) and the melt of metal nitrates.

Comparative examples a to D

A. 50 wt.% Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Rb0.15Mo12O48.25+50 wt.% SiO2.

Century 50 wt.% Ni5.0Mg2.0Fe1.8Bi0.45Cr0.1Rb0.15Mo12O46.6+50 wt.% SiO2.

C. 50 wt.% Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1K0.15Mo12O48.4+50 wt.% SiO2.

D. 50 wt.% Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Cs0.15Mo12O48.4+50 wt.% SiO2.

Applying the method of preparation described above in Example 1, the authors have prepared several other catalysts containing one or more components chromium, cerium or rubidium.

In comparative examples C and D cesium (CsNO3, 2.797 g) and potassium (KNO3, 1.458 g) respectively replaced by RB.

Comparative example F:

50 wt.% Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15Mn1.0Mo12O49.4+50 wt.% SiO2

In this catalyst, prepared as described above in example 1, was added manganese as Mn(NO3)2(32.699 g 51.1% solution).

Comparative example F:

50 wt.% Ni5.0Mg 2.0Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15Pd0.1Mo12O48.5+50 wt.% SiO2

In this catalyst, prepared as described above in example 1, is added to the noble metal palladium as Pd(NO3)2(2.2 g).

Comparative example G:

50 wt.% Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15V0.5Mo12O49.65+50 wt.% SiO2

In this catalyst, prepared as described above in example 1, added vanadium in the form of NH4VO3(5.514 g).

Comparative example H:

50 wt.% Ni5.0Mg2.0Fe1.8Bi0.45CE0.9Cr0.3Pb0.15Mo12O47.2+50 wt.% SiO2

This catalyst was prepared as described in example 1. However, at the atomic level the molar amount of cerium plus the molar amount of chromium was equal to the molar amount of bismuth. The set of components for preparation of the catalyst was as follows: Fe(NO3)3N2O (72.939 g), Ni(NO3)26N2O (145,83 g)., Mg(NO3)26N2O (51.434 g), Bi(NO3)35H2O (21.894 g), RbNO3(2.219 g) and (NH4)2Ce(NO3)6(16.496 g of 50% solution), was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (212.504 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(3.009 g) in 20 ml of water. For the eat was added silica gel (871.08 g 28.75% Zola SiO 2) and the melt of metal nitrates.

Comparative example I:

50 wt.% Ni5.0Mg2.0Fe1.8Bi0.45Ce0.1Cr0.1Rb0.15Mo12O46.8+50 wt.% SiO2

This catalyst was prepared as described in example 1. However, at the atomic level, the number of cerium plus the amount of chromium was less than the amount of bismuth. The set of components for preparation of the catalyst was as follows: Fe(NO3)3N2On (73.642 g), Ni(NO3)26N2On (147.236 g), Mg(NO3)26N2On (51.93 g), Bi(NO3)35H2O (22.105 g), RbNO3(2.24 g), (NH4)2Ce(NO3)6(11.104 g of 50% solution), was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (214.553 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(1.013 g) in 20 ml of water. Then was added silica gel (871.08 g 28.75% Zola SiO2) and the melt of metal nitrates.

Comparative example J:

50 wt.% Ni5.0Mg2.0Fe1.8Bi2.0Ce0.9Cr0.1Rb0.15Mo12O46.8+50 wt.% SiO2

This catalyst was prepared as described in example 1. However, at the atomic level, the number of cerium plus the amount of chromium was less than the amount of bismuth. The set of components for preparation of the catalyst was as follows: Fe(NO3)3N2O (61.264 g), Ni(NO3)2 6H2O (122.488 g), Mg(NO3)26N2On (43.201 g), Bi(NO3)35H2O (81.732 g), RbNO3(1.863 g), (NH4)2CE(NO3)6(83.136 g of 50% solution), was fused with ˜70°in the glass with a volume of 1000 ml Heptamolybdate ammonium (AMN) (178.49 g) was dissolved in 310 ml of distilled water. To this solution was added a solution of CrO3(0.843 g) in 20 ml of water. Then was added silica gel (871.08 g 28.75% 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/hour). 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 collected in a bubble scrubber 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 at 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 by approximately 200 g of distilled water. Sample 2-butanone was used as internal standard in ˜50 g aliquot of the diluted solution. Samples n is 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 (see table).

When

measures
The composition of the active phaseFull CONV. With3=CONV. in ANSat. on AN
1Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15Mo12O45.498.880.081.0
2Ni2.5Mg2.0Co2.5Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15Mo12O48.499.281.882.5
3Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Li0.3Rb0.15Mo12O48.5598.879.981.4
4Ni2.5Mg2.0Co2.5Fe1.8Bi0.45Ce0.9Cr0.1P0.1Rb0.15Mo12O48.9599.680.981.2
5Ni5.0Mg2.0Co2.5Fe1.8Bi0.45Ce0.9Cr0.1Na0.2Rb0.15Mo12O48.599.681.081.3
6Ni5.0Mg2.0Co2.5Fe1.8Bi0.45Ce0.9Cr0.1P0.1Rb0.15Mo12O48.6599.682.382.6
AndNi5.0Mg2.0Fe1.8Bi0.45Ce0.9Rb0.15Mo12O48.2599.479.379.9
InNi5.0Mg2.0Fe1.8Bi0.45Cr0.1Rb0.15Mo12O46.691.275.883.1
Ni5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1K0.15Mo12O48.499.777.677.8
DNi5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Cs0.15Mo12O48.496.869.672.0
ENi5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15Mn1.0Mo12O49.497.378.078. 6
FNi5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15Pd0.1Mo12O48.99.378.781.4
GNi5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.1Rb0.15V0.5Mo12O49.6596.476.879.7
HNi5.0Mg2.0Fe1.8Bi0.45Ce0.9Cr0.3Rb0.15Mo12O47.293.577.983.3
INi5.0Mg2.0Fe1.8Bi0.45Ce0.1Cr0.1Rb0.15Mo12O46.894.974. 478.5
JNi5.0Mg2.0Fe1.8Bi2.0Ce0.9Cr0.1Rb0.15Mo12O46.897.778.880.7
Notes:

1. All tested catalysts contained 50% of the active phase and 50% SiO2.

2. Full conversion With3=" means the conversion of propylene per pass (in mol. percent in all products.

3. "CONV. in AN" means the conversion of propylene per pass (in mol. percent) in Acrylonitrile.

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.

The composition of the catalyst according to the present invention is unique in that it contains rubidium, cerium, chromium, magnesium, iron, bismuth, molybd is n and at least one of the elements - Nickel or Nickel and cobalt with substantial absence of manganese, a noble metal and vanadium. This combination of elements in the proportions shown in the invention, not previously used in any catalyst of oxidative ammonolysis. As shown in the table, the catalyst of the present invention shows a higher activity in the reaction of oxidative ammonolysis of propylene to Acrylonitrile, than the catalysts with similar (but not exactly) combinations of elements proposed previously. More specifically, the catalysts containing rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and at least one element of Nickel or Nickel and cobalt with substantial absence of manganese, a noble metal and vanadium showed a higher complete conversion, the higher the conversion to Acrylonitrile in combination with the high selectivity of the formation of Acrylonitrile 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 can 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 kata is Isadora, suitable for oxidative ammonolysis of unsaturated hydrocarbons to the corresponding unsaturated nitrile containing the catalytically active complex oxides, including oxides of rubidium, cerium, chromium, magnesium, iron, bismuth, molybdenum and at least one of Nickel or Nickel and cobalt, in which the relationships of the elements represented by the following General formula:

RbaCebCrcMgdAeFefBigMo12Ox,

where And represents Ni or the combination of Ni and Co,

and equal to from about 0.01 to about 1,

b is equal to from about 0.01 to about 3,

equals from about 0.01 to about 2,

d is equal to from about 0.01 to about 7,

e is equal to from about 0.01 to about 10,

f is equal to from about 0.01 to about 4,

g is equal to from about 0.01 to about 4,

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

the "b" + "C" is greater than "g", and the catalyst contains manganese, precious metal or vanadium, and

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, in which b is greater than C.

3. The catalyst composition according to claim 1 which additionally includes phosphorus.

p> 4. The catalyst composition according to claim 1, which further comprises at least one of the elements - potassium, cesium, sodium, or mixtures thereof.

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

6. The catalyst composition according to claim 1, which includes silica gel with average sizes of colloidal particles from about 8 nm to about 100 nm.

7. A catalyst composition suitable for the oxidative ammonolysis of unsaturated hydrocarbons to the corresponding unsaturated nitrile containing the catalytically active complex oxides, including oxides of rubidium, cerium, chromium, iron, bismuth, molybdenum and at least one of Nickel or Nickel with cobalt, magnesium, and optionally one of the elements phosphorus, antimony, tellurium, sodium, lithium, potassium, cesium, thallium, boron, germanium, tungsten, calcium, zinc, rare earth elements, or mixtures thereof, and the relative ratios of these elements are represented by the following General formula:

RbaCebCrcMgdAeFefBigYhMo12Ox,

where And represents Ni or the combination of Ni and Co,

Y represents at least one element of P, Sb, Te, Li, Na, K, Cs, Tl, In, Ge, W, Ca, Zn, and rare earth element or mixtures thereof,

and equal to from about 0.01 to about 1,

b is equal to from prima is but 0.01 to about 3,

equals from about 0.01 to about 2,

d is equal to from about 0.01 to about 7,

e is equal to from about 0.01 to about 10,

f is equal to from about 0.01 to about 4,

g is equal to from about 0.01 to about 4,

h is equal to from 0 to about 3,

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

the "b" + "C" is greater than "g", and the catalyst contains manganese, precious metal or vanadium, and 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, in which b is greater than C.

9. The catalyst composition according to claim 7, which further phosphorus is present.

10. The catalyst composition according to claim 7, in which in addition there is at least one of the elements - potassium, cesium, sodium, or mixtures thereof.

11. The catalyst composition according to claim 7, in which the carrier is 30 to 70 wt.% catalytic Converter.

12. The catalyst composition according to claim 7, which includes an optional silica gel with average sizes of colloidal particles from about 8 nm to about 100 nm.

13. 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 value when the temperature and pressure specified olefin gas containing molecular oxygen and ammonia in the presence of a catalyst containing a catalytically active complex oxides, including oxides of rubidium, cerium, chromium, iron, bismuth, molybdenum and at least one of Nickel or Nickel with cobalt, magnesium, and optionally one of the elements phosphorus, antimony, tellurium, sodium, lithium, potassium, cesium, thallium, boron, germanium, tungsten, calcium, zinc, rare earth elements, or mixtures thereof, and the ratio of these elements is represented by the following General formula:

RbaCebCrcMgdAeFefBigYhMo12Ox,

where And represents Ni or the combination of Ni and Co,

Y represents at least one element of P, Sb, Te, Li, Na, K, Cs, Tl, In, Ge, W, Ca, Zn, and rare earth element or mixtures thereof,

and equal to from about 0.01 to about 1,

b is equal to from about 0.01 to about 3,

equals from about 0.01 to about 2,

d is equal to from about 0.01 to about 7,

e is equal to from about 0.01 to about 10,

f is equal to from about 0.01 to about 4,

g is equal to from about 0.01 to about 4,

h is equal to from 0 to about 3,

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

the "b" + "C" is greater than "g", and ka is alistar does not contain manganese, precious metal or vanadium, and a carrier selected from the group consisting of silica gel, aluminum oxide, zirconium oxide, titanium oxide or mixtures thereof.

14. The method according to item 13, wherein b is greater than C.

15. The method according to item 13, wherein h is equal to 0.

16. The method according to item 13, wherein the catalyst is additionally present phosphorus.

17. The method according to item 13, wherein the catalyst is present in at least one of the elements - potassium, cesium, sodium, or mixtures thereof.

18. The method according to item 13, wherein the carrier comprises from about 30 to 70 wt.% catalytic Converter.

19. The method according to item 13, wherein the catalyst contains silica gel with average sizes of colloidal particles from about 8 nm to about 100 nm.



 

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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.

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21 cl, 2 tbl, 8 ex

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The invention relates to a method for producing olefin-unsaturated NITRILES by the reaction of lower alkanes or alkenes with oxygen and ammonia in the gas phase in the presence of water vapor and a suitable catalyst at elevated temperature in the ammoxidation reactor with the formation at the exit of the hot gaseous stream comprising nitrile, unreacted reagents and by-products, followed by passing hot gaseous flow through the reverse jet scrubber, in which the hot gaseous stream is rapidly cooled, as a result of its contact with the cooling liquid injected countercurrent to the direction of movement of the specified gas flow, with the removal of ammonia, when this gaseous stream is passed through a reverse jet scrubber provided with such a speed that allows you to change to reverse the direction of flow of the injected coolant by evaporation of a part of the injected coolant

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.

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9 cl, 1 tbl

FIELD: chemical technology.

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EFFECT: improved manufacturing method.

13 cl, 19 ex

FIELD: organic chemistry, chemical technology.

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EFFECT: improved producing method.

21 cl, 2 tbl, 8 ex

FIELD: industrial organic synthesis.

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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
The invention relates to a method for producing a tin-containing vanadium-antimony catalysts suitable for the catalytic ammoxidation3-C5-paraffins or olefins, more specifically, to obtain catalysts for the ammoxidation of propane or isobutane, or propylene, or isobutylene with obtaining the appropriate,-unsaturated mononitriles, Acrylonitrile or Methacrylonitrile

FIELD: chemistry.

SUBSTANCE: invention refers to high metal catalyst compositions, production and application thereof in hydrotreating, specifically in hydrodesulfurisation and hydrodenitrogenating. Described is carrier-free catalyst composition containing one or more metals of VIb group, one or more metals of VIII group and refractory oxide material which contains at least 50 wt % of oxide-based titanium dioxide. Described is production method of catalyst compositions implying that one or more compounds of metal of VIb group is combined with one or more compounds of metal of VIII group and with refractory oxide material containing titanium dioxide with proton liquid and optionally alkaline compound; and catalyst composition is recovered by following precipitation. Described is application of composition described above or produced by method described above, moulded and sulphided if necessary, in hydrotreating of hydrocarbon raw materials.

EFFECT: higher activity of catalyst composition.

15 cl, 8 tbl, 16 ex

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