Catalytic composition (options) and a olefin conversion process involving it

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

 

The scope of the invention

The present invention relates to an improved catalyst which is used in the ammoxidation process of unsaturated hydrocarbons to the corresponding unsaturated nitrile. In particular, the present invention is directed to an improved process and catalyst for ammoxidation of propylene and/or isobutylene to Acrylonitrile and/or Methacrylonitrile respectively. More specifically, the invention relates to a new and improved catalyst for the ammoxidation process, comprising a complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one component made of Nickel or magnesium and at least one component of lithium, sodium, potassium, rubidium or thallium.

Description of the prior art

There are many patents related to the production of Acrylonitrile using a fluidized bed bismuth-molybdenum-iron catalysts. In particular, known GB 1436475; US 4766232; 4377534; 4040978; 4168246; 5223469 and 4863891, each focused on a bismuth-molybdenum-iron catalysts, which can be promoutirovanie elements of Group II in case of receipt of Acrylonitrile. In addition, US 4190608 reveals a similar promotion bismuth-molybdenum-iron catalyst for oxidation of olefins. US 5093299 and 5212137 focused on the process of promotion is of bismuth-molibdeno catalyst, that leads to high yields of Acrylonitrile.

Catalysts containing the oxides of iron, bismuth and molybdenum promoted the corresponding elements as described in the aforementioned patents have long been used for the conversion of propylene at elevated temperatures and in the presence of ammonia and oxygen (usually in the form of air) in Acrylonitrile.

The present invention is the development of a new catalyst that includes a unique combination of promoters, in order to better carry out the catalytic amoxicilina propylene, isobutylene or mixtures thereof in Acrylonitrile, Methacrylonitrile and their mixture, respectively.

The invention

The present invention is directed to an improved catalyst and process for the ammoxidation of propylene and/or isobutylene to Acrylonitrile and/or Methacrylonitrile respectively. The present invention is the development of a new catalyst, which is characterized by the following empirical formula:

AaBbCwithFedBieCofCegSbhMomOx

where a represents at least one of Cr, P, Sn, Te, In, Ge, Zn, In, Mn, Ca, W, or a mixture thereof

In represents at least one of Li, Na, K, Rb, Cs, Tl or a mixture thereof

With represents at least one of Ni, Mg or their mixture is

and has a value from 0 to 4.0

b has a value from 0.01 to 1.5

C has a value from 1.0 to 10.0

d has a value from 0.1 to 5.0

e has a value from 0.1 to 2.0

f has a value from 0.1 to 10.0

g has a value from 0.1 to 2.0

h has a value from 0.1 to 2.0

m has a value of from 12.0 to 18.0

and x is a number determined in accordance with the valence requirements of the other elements present.

The present invention is also directed to a process for conversion of olefins selected from the group consisting of propylene, isobutylene or mixtures thereof in Acrylonitrile, Methacrylonitrile and 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, where the catalyst has the empirical formula given above.

A detailed description of the invention

The present invention is directed to the development of the ammoxidation catalyst comprising a complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of Nickel or magnesium and at least one of lithium, sodium, potassium, rubidium or thallium, characterized by the following empirical formula:

AaBbCcFedBieCof CegSbhMomOx

where a represents at least one of Cr, P, Sn, Te, In, Ge, Zn, In, Mn, Ca, W, or a mixture thereof

In represents at least one of Li, Na, K, Rb, Cs, Tl or a mixture thereof

With represents at least one of Ni, Mg or mixtures thereof

and has a value from 0 to 4.0

b has a value from 0.01 to 1.5

C has a value from 1.0 to 10.0

d has a value from 0.1 to 5.0

e has a value from 0.1 to 2.0

f has a value from 0.1 to 10.0

g has a value from 0.1 to 2.0

h has a value from 0.1 to 2.0

m has a value of from 12.0 to 18.0

and x is a number determined in accordance with the valence requirements of the other elements present.

Component "a" is an optional element in the above-described catalyst. If "A" is present, then "a" is preferably selected from the group consisting of Cr, P, Ge, Ca, or mixtures thereof. In the preferred embodiment of the present invention "B" is chosen from one or more of Li, Na, K, Cs or mixtures thereof, especially preferred are Li, Cs or mixtures thereof. In the preferred embodiment of the present invention "With" is a mixture of Ni and Mg, that is, the catalyst contains both elements and Ni and Mg.

In other preferred embodiments of the present invention "and" can independently be in the range from about 0.1 to 4.0, especially predpochtite the flax in the range of from about 0.1 to 3.0; "b" can independently be in the range from about 0.05 to 1.2, particularly preferably approximately in the range of from 0.1 to 1.0; "C" can independently be in the range from about 2.0 to 9.0, particularly preferably in the range of from about 2.0 to 8.0; "d" can independently be in the range from about 0.5 to 5.0, particularly preferably in the range of from about 1.0 to 4.0; the "e" can independently be in the range from about 0.1 to 1.5, particularly preferably in the range of from about 0.1 to 1.0; "f" may independently be in the range from about 1.0 to 7.0, particularly preferably in the range of from about 1.0 to 1.5; "g" may independently be approximately in the range of from 0.3 to 1.5, particularly preferably in the range of from about 0.3 to 1.2; "h" can independently be approximately in the range of from 0.3 to 1.5, particularly preferably approximately in the range of from 0.3 to 1.2; and "m" can independently be in the range from about 13.0 to 16.0.

The catalyst in accordance with the present invention can be used as deposited on a substrate, and nenalezena on a substrate. Preferably the catalyst is applied on the silicon dioxide, aluminum oxide, Zirconia, titanium dioxide or mixtures thereof, particularly preferably as a substrate for catalyst use silicon dioxide. The amount of substrate to catalyst m is may vary. Typically, the substrate is from about 30 to 70 percent of the total weight of the catalyst, more preferably approximately 50 percent of the total weight of the catalyst.

Examples of catalytic compositions in accordance with the present invention include:

To0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5Ce1.0Sb0.5Mo13.6Ox+50 wt.% SiO2

K0.2Ni4.5Mg1.5Fe2.0Bi0.5Ca0.2Co1.7Ce0.5Sb0.5Mo13.6Ox+50 wt.% SiO2

Cs0.1K0.1Mg2.0Fe2.0Bi0.5Co6.2Ce0.5Sb0.3Mo13.6Ox+50 wt.% SiO2

Cs0.15Ni3.0Mg2.5Fe1.5Bi0.3Co3.0Ce0.5Sb0.5W0.2Mo13.0Ox+50 wt.% SiO2

Cs0.15Ni2.5Mg2.5Fe1...5Bifor 0.3Li1.0.2Co2.8Ce1.0Sb0.5Mo13.0Ox+50 wt.% SiO2

Cs0.1K0.1Ni5.0Mg2.5Fe1.5Bi0.3P0.2Co1.0Ce0.5Sbo.5MoOOx+50 wt.% SiO2

Cs0.1K0.1Ni4.0Mg2.0Fe2.0Bi0.5Co2.2CE0.3Cr0.2Sb0.3Mo13.6Ox+50 wt.% SiO2

The catalysts in accordance with the present invention can be obtained by using any of numerous methods of making catalysts, it is known that the average specialist. For example, the catalyst may be obtained by joint precipitation of the various ingredients. The mass obtained after co-deposition may then be dried and pulverized to an appropriate particle size. An alternative material, obtained by joint precipitation, can be suspended and sprayed dry in accordance with conventional technology. The catalyst may be extruded in the form of granules or shaped in the form of needles in oil, as is known from the prior art. Alternative components of the catalyst can be mixed with the substrate in the form of a suspension, followed by drying, or they can be deposited by impregnation on the silicon dioxide or other substrate. Specific methods of obtaining catalysts described in US 5093299; 4863891 and 4766232.

Components of catalyst (i.e. at least one of Cr, P, Sn, Te, In, Ge, Zn, In, Mn, Ca) W, or mixtures thereof, can be obtained from any available source. For example, cobalt, Nickel and magnesium can be introduced into the catalyst using a nitrate salt. Additionally, the magnesium may be introduced into the catalyst as insoluble carbonate or hydroxide, which, if the heat treatment gives the oxide. Phosphorus can be introduced into the catalyst in the form of alkali metal salt or alkaline earth metal salt or ammonium salt, but preferably it is introduced in the form of phosphoric acid. Calcium can be is added through the preliminary formation of calcium molybdate or impregnated or otherwise, known from the prior art.

Typically, the component b of the catalyst (i.e. at least one of Li, Na, K, Rb, Cs, Tl or a mixture thereof) may be introduced into the catalyst in the form of the oxide or in the form of salt, which upon calcination yields the oxide. Preferably such salts, such as nitrates, which are easily accessible and readily soluble, is used as a means of introducing the element a in the catalyst.

Bismuth can be introduced into the catalyst as an oxide or salt, which upon calcination yields the oxide. Soluble salts, which are easily dispersed, but form stable oxides by heat treatment is preferable. Particularly preferred source for the introduction of bismuth is bismuth nitrate, which was dissolved in a solution of nitric acid.

To enter the iron component in the catalyst, it is possible to use any compound of iron, which, when the calcination will lead to oxides. As other elements of the water-soluble salts are preferred, in order to facilitate the process of their homogeneous dispersion within the catalyst. Most preferred is iron nitrate.

Molybdenum component of the catalyst may be introduced through any oxide of molybdenum, such as dioxide, trioxide, pentoxide, niobium or heptaoxide. However, it is preferable that in ka is este source of molybdenum was used hydrolyzable or decaying salt of molybdenum. The most preferred source product is heptamolybdate ammonium.

The catalysts obtained by mixing an aqueous solution of heptamolybdate ammonium colloidal solution of silicon dioxide, to which is added a suspension containing compounds, preferably nitrates of other elements. The solid material is then dried, denitrification and calcined. Preferably, the catalyst is dried by spraying at a temperature of between 110°C to 350°C, preferably 110°to 250°S, most preferably 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 calcining(burning) is carried out at a temperature between 300°700°C, preferably in the range from 350°650°C.

The catalysts in accordance with the present invention is applicable in the ammoxidation processes for the conversion of an olefin selected from the group consisting of propylene, isobutylene or mixtures thereof in Acrylonitrile, Methacrylonitrile and 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 catalyst.

Preferably the ammoxidation reaction is carried out in a reactor with pseudowire the second layer, although other types of reactors, such as reactor separation line, are also used. The fluidized bed reactor for the production of Acrylonitrile are known in the prior art, for example, the reactor described in US 3230246 is suitable for the process.

Conditions of the ammoxidation reaction is also well known from the prior art, as known from US 5093299; 4863891; 4767878 and 4503001. Usually the ammoxidation process is carried out by contacting propylene or isobutylene in the presence of ammonia and oxygen in the fluidized bed of the catalyst at elevated temperature to obtain Acrylonitrile or Methacrylonitrile. Can be used any source of oxygen. For economic reasons, however, it is preferable to use the air. The usual molar ratio of oxygen to olefin in the feed must 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 feedstock in the reaction time may range from 0.5:1 to 5:1. In fact, there is no upper limit for the olefin - ammonia, but there is no reason to exceed this ratio as 5:1 for economic reasons. Preferential treatment of raw materials to the catalyst of the present invention to obtain Acrylonitrile amount of ammonia relative to p is opilio from 9:1 to 1.3:1 and air with respect to propylene from 8.0:1 to 12.0:1.

The reaction is carried out in the temperature range from about 260°to 600°With preferred ranges are between 310°500°especially preferred from 350°480°C. the contact Time, although not critical, is generally in the range of from 0.1 to 50 seconds, preferably the contact time is 1-15 seconds.

The reaction products can be strangled and purified by any of the methods known from the prior art. One such method includes the gas cleaning flue gases from the reactor with cold water or an appropriate solvent to remove the reaction products and then to clean the reaction product by distillation.

The main use of the catalyst in accordance with the present invention is the ammoxidation of propylene to Acrylonitrile. However, the present catalyst can also be used for the oxidation of propylene to acrylic acid. Such processes are usually two-stage process in which propylene is converted into the presence of a catalyst mainly acrolein in the first stage, and convert acrolein in the presence of a catalyst mainly in acrylic acid in the second stage. The catalyst described in this invention is suitable for use on both stages.

A specific embodiment of the

To explain the present izopet the tion, the following examples, which are illustrative only.

Example: a Catalyst of the formula K0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3...5Ce1.0Sb0.5Mo13.6Aboutx+50 wt.% SiO2prepared as follows: 196,49 g heptamolybdate ammonium (AMN) is dissolved in 400 ml of water. Add 625 g of a colloidal solution of silicon dioxide containing 40 wt.% SiO2in relation to the ASM solution, and then adding 5.96 g Sb2O3. Finally, add a mixture of molten nitrates of metals containing: 66.12 g Fe (NO3)2N2O, 71.39 grams Ni (NO3)2·6H2O, 83.36 g With (NO3)2·6N2O, 41.96 g of Mg (NO3)2·6N2O, 19.85 g of Bi (NO3)3·5H2O, 1.66 g KNO3and 89.73 g CE (NH4)2(NO3)6·6N2O in the form of a 50%aqueous solution. The obtained suspension is stirred and then dried with a spray that gives 479 g of catalyst. The catalyst is subjected to heat treatment for 3 hours at 290°and then 3 hours at 425°and finally 3 hours at 600°to give a catalyst.

Comparative Examples a to G: Using the preparation described above were similarly obtained several other catalysts, each of which exclude one or more elements, such as cobalt, cerium or antimony of the composition. The composition is these catalysts are given in Table 1.

To identify illustrate implement the declared cobalt, cerium and Sarmanovo promoted catalysts to similar catalysts, which exclude one or more of these elements, all the catalysts were evaluated in a similar reaction conditions. Raw materials containing a mixture of 1C3=/1.2NH3/9.5 air is passed through the catalyst in the tube 1" diameter at approximately 430°C, 10 psig and 0.09 mass/mass hour. The resulting Acrylonitrile collected and measured.

Table 1
ExamplesComposition of catalyst (all songs+50 mass % SiO3)In common With3=conversionConversion of Acrylonitrile
ExampleTo0.2Ni3.0Mg2.0Fe3.0Bi0.5Co3.5Ce1.0Sb0.5Mo13.6Ox98.0%79.8%
Composition AndK0.2Ni3.0Mg2.0Fe2.0Bi0.5-Ce1.0Sb0.5Mo13.6Ox71.7%56.9%
CompositionK0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5-Sb0.5Mo13.6Ox80.4%64.1%
The composition is K0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5Ce1.0-Sb0.5Mo13.6Ox97.1%76.2%
Composition DK0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5-Mo13.6Ox85.7%67.3%
Composition EK0.2Ni3.0Mg2.0Fe2.0Bi0.5-Sb0.5Mo13.6Ox79.6%64.2% -
ExampleK0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5Ce1.0Sb0.5Mo13.6Ox98.0%79.8%
Composition FTo0.2Ni3.0Mg2.0Fe2.0Bi0.5-CE1.0-Mo13.6Ox85.1%66.8%
Composition GK0.2Ni3.0Mg2.0Fe2.0Bi0.5---Mo13.6Ox79.7%60.4%
Comments:

1. "In common With3=the conversion rate" represents the mole percent conversion of propylene to all products in a single pass.

2. "Conversion of Acrylonitrile" mole percent conversion of propylene to Acrylonitrile in a single pass.

The composition of the catalyst in accordance with the present invention is unique in that it contains three promoted item, namely, cobalt, cerium and antimony, which has not previously been used in combination in a single catalytic composition for the ammoxidation process. As illustrated in Table 1, a process for ammoxidation of propylene to Acrylonitrile, the catalyst in accordance with the present invention showed better results than prior known catalyst not containing none, one or two of these elements. More specifically, the catalyst containing cobalt, cerium and antimony, showed higher overall conversion and a higher conversion to Acrylonitrile, when propylene is subjected to ammoxidation over this catalyst at elevated temperature in the presence of ammonia and air.

While the present invention has been described on the example of a specific embodiment of the above, it is evident that many alternatives, modifications and variations will be available specialists in this field in the light of the preceding description. Accordingly, the present invention is not intended to cover all such variations, modifications and changes which come within the boundaries of the claims.

1. Catalytic composition comprising a complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of Nickel or magnesium and at least one of whether the Oia, sodium, potassium, rubidium or thallium, the following empirical formula:

AaBbCcFedBieCOfCegSbhMonOx,

where a represents at least one of Cr, P, Sn, Te, In, Ge, Zn, In, Mn, Ca, W, or mixtures thereof;

In represents at least one of Li, Na, K, Rb, Cs, Tl or a mixture thereof;

With represents at least one of Ni, Mg or mixtures thereof;

and has a value from 0 to 4.0;

b has a value from 0.01 to 1.5;

C has a value from 1.0 to 10.0;

d has a value from 0.1 to 5.0;

e has a value from 0.1 to 1.0;

f has a value from 0.1 to 10.0;

g has a value from 0.1 to 2.0;

h has a value from 0.1 to 2.0;

m has a value from 13.0 to 16.0;

x is a number determined in accordance with the valence requirements of the other elements present.

2. Catalytic composition comprising a complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of Nickel or magnesium and at least one of lithium, sodium, potassium, rubidium or thallium, the following empirical formula:

AaBbCcFedBieCofCegSbhMonOx,

where a represents at least one of Cr, P, Sn, Te, In, Ge, Zn,In, Mn, Ca, W, or mixtures thereof;

In represents at least one of Li, Na, K, Rb, Cs, Tl or a mixture thereof;

With represents at least one of Ni, Mg or mixtures thereof;

and has a value from 0 to 4.0;

b has a value from 0.01 to 1.5;

C has a value from 1.0 to 10.0;

d has a value from 0.1 to 5.0;

e has a value from 0.1 to 2.0;

f has a value from 0.1 to 1.5;

g has a value from 0.1 to 2.0;

h has a value from 0.1 to 2.0;

m has a value from 13.0 to 16.0;

x is a number determined in accordance with the valence requirements of the other elements present.

3. Catalytic composition comprising a complex of catalytic oxides of iron, bismuth, molybdenum, cobalt, cerium, antimony, at least one of Nickel or magnesium and at least one of lithium, sodium, potassium, rubidium or thallium following empirical formula:

AaBbCcFedBieCofCegSbhMomOx,

where a represents at least one of Cr, P, Sn, Te, In, Ge, Zn, In, Mn, Ca, W, or mixtures thereof;

In represents at least one of Li, Na, K, Rb, Cs or mixtures thereof;

With represents at least one of Ni, Mg or mixtures thereof;

and has a value from 0 to 4.0;

b has a value from 001 to 1.5;

C has a value from 1.0 to 10.0;

d has a value from 0.1 to 5.0;

e has a value from 0.1 to 2.0;

f has a value from 0.1 to 10.0;

g has a value from 0.1 to 2.0;

h has a value from 0.1 to 2.0;

m has a value of from 12.0 to 18.0;

x is a number determined in accordance with the valence requirements of the other elements present.

4. The catalytic composition according to any one of claims 1 to 3, which is deposited on inert support selected from the group consisting of silicon oxide, aluminum oxide, zirconium dioxide, titanium dioxide and mixtures thereof.

5. The catalytic composition according to any one of claims 1 to 5, which is a mixture of Ni and Mg.

6. 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 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 oxide catalyst having the formula

AaBbCcFedBieCofCegSbhMonOx,

where a represents at least one of Cr, P, Sn, Te, In, Ge, Zn, In, Mn, Ca, W, or mixtures thereof;

In represents at least one of the C Li, Na, K, Rb, Cs, Tl or a mixture thereof;

With represents at least one of Ni, Mg or mixtures thereof;

and has a value from 0 to 4.0;

b has a value from 0.01 to 1.5;

C has a value from 1.0 to 10.0;

d has a value from 0.1 to 5.0;

e has a value from 0.1 to 2.0;

f has a value from 0.1 to 10.0;

g has a value from 0.1 to 2.0;

h has a value from 0.1 to 2.0;

m has a value of from 12.0 to 18.0;

x is a number determined in accordance with the valence requirements of the other elements present.

7. The method according to claim 6, characterized in that the catalyst deposited on an inert substrate selected from the group consisting of silicon oxide, aluminum oxide, zirconium dioxide, titanium dioxide and mixtures thereof.

8. The method according to claim 6, characterized In that, selected from the group consisting of Na, Li, K, Cs or mixtures thereof.

9. The method according to claim 6, characterized in that is a mixture of Ni and Mg.



 

Same patents:

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

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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

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FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing acrylic acid and selective oxidation of propylene to acrolein. Method involves carrying out reaction of propylene with oxygen in the first zone reaction with the first catalyst corresponding to the following formula: AaBbCcCadFeeBifMo12Ox wherein A means Li, Na, K, Rb and Cs and their mixtures also; B means Mg, Sr, Mn, Ni, Co and Zn and their mixtures also; C means Ce, Cr, Al, Sb, P, Ge, Sn, Cu, V and W and their mixtures also wherein a = 0.01-1.0; b and e = 1.0-10; c = 0-5.0 but preferably 0.05-5.0; d and f = 0.05-5.0; x represents a number determined by valence of other presenting elements. Reaction is carried out at enhanced temperature providing preparing acrylic acid and acrolein and the following addition of acrolein from the first reaction zone to the second reaction zone containing the second catalyst used for conversion of acrolein to acrylic acid. Method provides high conversion of propylene to acrylic acid and acrolein.

EFFECT: improved preparing method.

7 cl, 1 tbl, 5 ex

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The invention relates to copper-containing catalysts for low-temperature methanol synthesis at low pressure

The invention relates to oxidation catalysts, in particular catalysts for oxidative ammonolysis Ethylenediamine compounds based on metal oxides, the method thereof and method of oxidative ammonolysis of ammonolysis Ethylenediamine connections

The invention relates to catalysts and methods of hydroperiod of crude oil

The invention relates to the production of catalysts, namely the production of catalysts for the processes of dehydrogenation of alkylaromatic hydrocarbons

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: invention relates to hydrotreatment of different petroleum fractions with high content of straight-chain paraffins to yield product with high content of isoparaffins. Catalyst is prepared on the base of crystalline elemento-alumino-phosphates having specified structure via (i) preparing aqueous reaction mixture containing aluminum source, concentrated phosphoric acid, and one or two sources of substituting element selected from magnesium, zinc, silicon, cobalt, manganese, nickel, chromium, and also organic structuring compound constituting di-n-pentylamine or mixture thereof with other di-n-alkylamines and having following composition (in molar parts): R/Al2O3 0.5-2.0, P2O5/Al2O3 0.8-1.2, MOx/Al2O3 0.05-1.5, and H2O/Al2O3 15-200 followed by (ii)crystallization of thus prepared mixture.

EFFECT: increased activity and selectivity of catalyst with regard to formation of desired reaction products and preserved catalyst activity regarding hydrogenation of aromatics.

4 cl, 1 dwg, 14 ex

FIELD: catalysts of selective hydrogenation of alkynes of C4 fractions.

SUBSTANCE: proposed catalyst contains 1-30 mass-% of copper used as first active component, 0.001-5 mass-% of palladium used as second active component, at least 0.001-6 mass-% of one metal selected from Al, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as co-catalyst; the remainder being one carrier selected from aluminum oxide, silicon dioxide and titanium oxide. Method of production of catalyst includes impregnation of carrier calcined preliminarily with solutions of active components depending on their content in catalyst. Alkynes are removed from C4 fractions enriched with alkynes by means of selective hydrogenation with the use of said catalyst.

EFFECT: enhanced selectivity and stability of catalyst.

31 cl, 2 tbl, 13 ex

FIELD: cleaning waste gases from hydrocarbons; oil refining industry, petrochemical industry and other industries.

SUBSTANCE: proposed method includes oxidation with atmospheric oxygen at elevated temperature in presence of catalyst performed at temperature of 270-280°C in presence of cement-containing catalyst at the following composition of components, mass-%: copper oxide (CuO), 30-50; zinc oxide (ZnO), 19-30; manganese oxide (Mn3O4), 0.5-16; the remainder being technical calcium aluminate.

EFFECT: high degree of cleaning waste gases from hydrocarbons.

1 tbl

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