Method of producing hydrogen cyanide through catalytic oxidation in ammonia medium

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hydrogen cyanide through catalytic oxidation of starting material in ammonia medium. The oxidation method is carried out in ammonia medium of alcoholic starting material such as methanol, or nitrile starting material such as propionitrile, or mixture thereof. To form hydrogen cyanide, modified Mn-P catalyst is used, having the following empirical formula: MnaPlAbOx, where A is one or more elements K, Ca, Mo, Zn, Fe or combination thereof; a varies from 1 to 1.5; b varies from 0.01 to 1.0 and x is the total number of oxygen atoms, which is determined from the oxidation state of present elements. The invention also includes a catalyst for oxidation in ammonia medium.

EFFECT: catalyst has high activity.

13 cl, 2 tbl, 5 ex

 

1. The technical field to which the invention relates.

The present invention concerns a method of producing cyanide in the catalytic oxidation of ammonia environment using a modified catalyst Mn-P.

2. Description of the prior art,

Hydrogen cyanide (HCN) is a very important by-product of the synthesis of polyamide (nylon). It is used in the production of methyl methacrylate, nitryltriacetic acid (NTA, washing additive), herbicides, and to develop methylthiophenol acid (nutritional Supplement for animals), complexing agents and many other pure and specialized reagents. It is also used to extract gold from minerals. Annual production of HCN in the United States is about 700,000 tons. About 20% of that HCN is a by-product during the manufacture of Acrylonitrile (AN): more than 70% is produced by the method Androsova developed in the 1930-ies (DuPont company), while using a process patented by the company Degussa, is a relatively small number (less than 10%).

In the method, patented by the company Degussa, CH4and NH3react directly in ceramic tubes, coated with platinum. Since the reaction between CH4and NH3is strongly endothermic (equation 1), for it forms the Oia requires high temperatures (1200-1300°C); the necessary amount of heat is produced when fossil fuels are burned out tubes.

NH3+CH4→HCN+3H2(ΔHr=252 kJ/mol)(1)

As this process proceeds in the absence of air, excluded a number of adverse reactions. Moreover, the exiting gas is almost pure H2(96,2%) after removal of HCN and NH3. Chemical transformation of NH3in HCN is 80-85%, and chemical transformation of CH4in HCN is 90%.

In the method Androsova introduces the air in order to burn a small amount of CH4to provide the necessary heat for the reaction. Thus, obtaining HCN using the last method is the reaction occurring in the ammonia environment

NH3+2CH4+3,5 ° 2→HCN+CO2+5H2O (ΔHr= -474 kJ/mol)(2)

When using the method Androsova the process goes on and o adiabatically at a temperature of about 1100°C. the Optimum composition of the original product is determined as a compromise between selectivity chemical transformations NH3in HCN, which is preferable for high ratios of CH4/NH3when a fixed ratio of the air/fuel and the overall speed of receiving HCN, which is preferred for relatively low ratio of CH4/NH3. The contact time is very small (less than 1 millisecond), which prevents the decomposition ready HCN. A typical catalyst in the method Androsova consists of wire mesh, containing 90 wt%. Pt and 10 wt%. Rh. The valid lifetime of the catalyst is from 60 to 360 days. Approximately 65-70% of the ammonia is converted into HCN, and about 10% of the ammonia is converted into N2. In order to avoid decomposition of HCN gas products containing about 6-12% HCN, rapidly cooled to a temperature of 350-400°C in the recovery boiler.

In addition, HCN stands out as a by-product in the oxidation of propylene to Acrylonitrile in an ammoniacal medium in accordance with the following reaction:

CH2=CHCH3+3NH3+3O2→3HCN+6H2O (ΔHr= -273 kcal/mol)(3)

The amount of HCN produced as a by-product in the oxidation of propylene in the ammonia environment, associated with a particular number of resulting'AN. HCN is a valuable product, and sometimes the need for this product exceeds the number which is obtained in the oxidation of propylene in the ammonia environment. In this case, together with propylene in reactor loaded methanol, where it reacts with ammonia and oxygen on the catalyst to obtain AN HCN as follows:

CH3OH+NH3+O2→HCN+3H2O (ΔHr=-83 kcal/mol)(4)

However, the catalysts to obtain AN practiced more propylene than for methanol. In addition, the introduction of methanol in the initial mixture for the oxidation of propylene in the ammonia environment can reduce the viability of the catalyst.

Therefore, there is a need to separate production and AN HCN and to develop a more economical method for the production of HCN. In the method it is necessary to use a catalyst designed specifically for the production of HCN from methanol.

There are a number of known catalysts for the oxidation of methanol in ammonia environment based on complex oxides of metals, such as K0,006Bi0,45Feof 0.65Pa 0.1MoOx-50%SiO2that includes almost all the elements in the periodic table. However, only some of them have actually been tested for use in the oxidation reaction in an ammonia environment. Some of the known catalysts for the oxidation of ammonia to the environment and the properties of these catalysts are shown in table 1.

Table 1
The oxidation of methanol in ammonia environment using catalysts containing complex oxides
RoomThe composition of the catalystThe reaction conditionsCatalytic properties∗
1FeaCubSbcMOdMeeTefQgOx/SiO2
Me = V, W; Q = Mg, Zn, La, Ce, Al, Cr, Mn, Co, Ni, Bi, U, Sn
T=350-500°C O2:NH3:MeOH=2:1.1:1X=96-100%,
Y=79-93%
2RrXqTpZsFetSbuPvOx
R = IA and IB, PS, X = Bi, Te;
T = Cr, Co, Cu, Ce, Th, B, Sn;
Z = V, Mo, W
T=300-500°C O2:NH3:MeOH:H2O=2,1:1,2:1:2,25S=82-95%
Y=77-87%
3RrAaBibCecWdVeMofOx
R = Cr, Sb; A = K, Na, Rb, Cs, Tl, Sm, Ag, Cu
T=300-500°C O2:NH3:MeOH:H2O=2,1:1,2:1:2Y=54-72%
4FeaSbbQcRdOx
Q=V, Co, Ni, Cu, Mo, W, Bi;
R = B, P, K, Zn, Te
T=band 380-470°C O2:NH3:MeOH =1,4:1:1X=96-99 .8%,
Y=91-94%
5FeaSbbPcXdQeRfOx/SiO2
X = V, Mo, W; Q = Li, Na, K, Rb. Cs, Mg, Ca, La, Ce, Ti, Zr, Nb, Ta, Cr, Mn, Re, Co, Ni, Cu, Ag, Zn, Al, Sn, Pb;
R = B, As, Se, Te
T=350-500°C
O2:MeOH=1-10
NH3:MeOH=0,7-2,5
X=80-100%,
S=89-96%
Y=70-94%
6FeaSbbPcVdMoeCufWgXhYiZjO/SiO2
X = Mg, Zn, La, Ce, Al, Cr, Mn, Co,
Ni, Bi, U, Sn; Y = B, Te;
Z = Li, Na, K, Rb, Cs, Ca, Ba
T=band 380-470°C
About2:MeOH=1,3-1,5
NH3:MeOH=0,7-1,1
X=98-100%,
Y=78-94,5%

7FeaSbbPcVdMoeCufWgXhYiZjO/SiO2
X = Mg, Zn, La, Ce, Al, Cr, Mn, Co, Ni, Bi, U, Sn; Y = B, Te; Z = Li, Na, K, Rb, Cs, Ca, Ba
T=band 380-470°C
About2:MeOH=1,3-1,5
NH3:MeOH=1-1,3
X=97-100%
Y=80-92%
8FeaSbbPcMxOy
M = V, Mo
T=440-480°C O2:NH3:MeOH =1.6:1:1X=82-100%
S=93,2-94,7%
9FeaSbbPcVxCuyOzT = 440°C
About2:NH3:MeOH =1.5:1:1
Y = 94,5%
∗ - Chemical conversion of methanol, and S is the selectivity to HCN, Y - yield of HCN.

In the 1980s, Monsanto has done much of the experimental work related to the oxidation of methanol in ammonia environment, which were developed catalysts for the production of HCN from methanol-based phosphates of manganese (Mn1,25POx). Catalysts based on phosphates of manganese (Mn1,25POxvery simple to prepare and can provide up to 90% of output HCN from methanol. The process can take place in conditions that are close to the currently accepted conditions of obtaining'AN, and can be implemented when the existing plant'AN.

Therefore, the catalyst specifically designed for the production of HCN from methanol with increased yield, will have significant advantages compared to the catalysts used in existing technologies.

The INVENTION

The present invention is the creation of modified Mn-P catalysts for production of hydrogen cyanide (HCN). Modified Mn-P the catalyst according to the accordance with the present invention has the following empirical formula:

MnaP1AbOx

where A = one or more elements K, Ca, Mo, Zn, Fe or a combination thereof; and = from 1 to 1.5; b = from 0.01 to 1.0 and x is the total number of oxygen atoms determined by the degree of oxidation present elements.

The modified catalyst based on Mn-P is used for the oxidation of ammonia environment alcohols and/or NITRILES upon receipt HCN. This process uses a modified Mn-P catalyst, designed to produce HCN from alcohols, NITRILES or mixtures thereof at conditions close to the conditions that are typically used in current practice to produce AN of propylene. The preferred alcohol is methanol. Preferred NITRILES are propionitrile (PN) and acetonitrile (ACN). In the mixture may include a mixture of NITRILES or mixtures of NITRILES and alcohols. The process includes the transmission of the original product in the form of gas, or alcohol, or nitrile, or mixtures thereof, together with ammonia and oxygen in the reaction zone in the presence of the modified Mn-P catalyst.

To enhance the performance of unmodified Mn-P catalyst can be added accelerators, such as K, Ca, Mo, Zn, and Fe, as disclosed in U.S. patent 4457905. Modified Mn-P catalyst with the addition of K and Ca has a greater selectivity to HCN, the yield of HCN is 2-3% higher than the yield HCN when using the years of unmodified Mn-P catalyst. Mn-P catalyst modified with molybdenum (Mo), has a much higher activity than unmodified Mn-P catalyst, for a given loading of methanol requires a smaller amount of catalyst. Mn-P catalyst modified with zinc (Zn), has a higher activity and selectivity than the unmodified Mn-P catalyst, for a given load requires a smaller amount of catalyst supported on high value chemical conversion of methanol and provides a high yield of HCN.

In contrast to previous catalysts modified Mn-P catalysts in accordance with the present invention can be used in a wide range fed to the reactor source compounds, such as NITRILES or mixtures of NITRILES and alcohols. When submitting propionitrile as the original product Mn-P catalyst modified with iron (Fe), has a higher efficiency than unmodified Mn-P catalyst.

DETAILED description of the INVENTION

The present invention relates to a method for ammonium oxidation in the environment to cyanide source such products, such as alcohols, such as methanol, and/or NITRILES, such as propionitrile (PN) and acetonitrile (ACN), which includes the transmission referred to the original product with ammonia and oxygen or gas containing the m oxygen, in the reaction zone, which operates under oxidizing conditions in an ammonia environment and contains a catalytically effective amount of a modified Mn-P catalyst corresponding to the following empirical formula:

MnaPlAbOx,

where A = one or more elements K, Ca, Mo, Zn, Fe or a combination thereof; and = from 1 to 1.5; b = from 0.01 to 1.0 and x is the total number of oxygen atoms determined by the oxidation state of the elements present.

In a more restricted variants of embodiment of the invention the present invention relates to a method for oxidation of methanol to hydrogen cyanide ammonia environment, which involves feeding to a reactor operating under oxidizing conditions in an ammonia environment, the original product containing methanol, ammonia and oxygen or a gas containing oxygen, and where the area in which flows the oxidation reaction in an ammonia environment, includes a fluidized bed of catalyst for the oxidation of ammonium to the medium containing the modified Mn-P catalyst having the following empirical formula:

MnaP1AbOx

where A = one or more elements K, Ca, Mo, Zn, Fe or a combination thereof and = from 1 to 1.5; b = from 0.01 to 1.0 and x is the total number of oxygen atoms determined by the oxidation state of the elements present.

Usually modified Mn-P catalyst receive conventional pic is the means. Preferably the modified Mn-P catalyst was prepared according to the method disclosed in U.S. patent 4457905, according to which unmodified Mn-P dry catalytic material impregnated with various salts of metals. Various metals can also be introduced into a paste-like mixture before grinding or before spraying by dehydration of aqueous solutions of their soluble salts. In preferred embodiments, embodiments of the invention, a modified Mn-P catalyst is produced using the wet impregnation for the introduction of various metals such as Ca, K, Mo, Fe, and Zn from aqueous solutions of their soluble salts in unmodified Mn-P catalyst obtained in accordance with U.S. patent 4457905 and pre-dried at 200°C. After wet impregnation, it is preferable to use the process of roasting. The temperature of calcination can be from 850°C to 1000°C. the Contents of U.S. patent 4457905 included in this document as a reference.

Although the catalyst can be used in pure form, it is preferable to apply the catalyst to the substrate. Preferred are inert substrate, such as silicon (SiO2), titanium (TiO2), aluminum (Al2O3) and other commonly used substrates. Especially preferred is silicon. In the process of making the cat who lyst silicon preferably in two stages. First, a small amount of silicon is mixed with the active catalytic components, and the mixture is stirred for 1-3 hours at a temperature of from 80 to 100°C. then added to the remaining portion of the silicon substrate. This two-step addition of silicon improves the activity of the catalyst and increases the yield of HCN.

To compounds of manganese, which can be used include any compounds of manganese, which can be introduced into the catalyst. For preferred compounds include manganese acetate, manganese nitrate, manganese oxide, manganese chloride, and similar compounds.

To compounds of phosphorus, which can be used include any phosphorus compounds known in the art, including phosphorus oxide (Y), phosphoric acid, ammonium dihydrophosphate, ammonium phosphate and the like compounds.

Used conditions of the oxidation reaction in the ammonia environment are the conditions described in this area for oxidation of methanol in ammonia environment: characteristic temperature from 200 to 600°C, best results are obtained at a temperature of 250 to 550°C and the best results are obtained at temperatures from 300 to 500°C.

The molar ratio of the reactants in the reaction zone of oxidation in the ammonia environment is constant. Usually the molar ratio of ammonia and oxygen to m is tanoglu or nitrile close to the stoichiometric therefore, most of the reagents will be consumed in the reaction. Usually the ratio of ammonia to methanol or nitrile is from 0.7:1 to 2:1, preferably from 0.9:1 to 1.3:1. The use of excess ammonia is undesirable as ammonia, unreacted must be extracted and reused or put to waste.

The preferred source of oxygen is air because of its cheapness; but you can also use pure oxygen or oxygen-enriched air. Avoid flammable mixtures.

May be inert diluents commonly used in laboratories, not in industry. The exception is nitrogen, which is usually served together with the air supplies oxygen to the reaction zone.

Although the preferred mode of operation is to work in the fluidized bed, the process may well be carried out in a fixed bed, fluidized bed, a moving layer. Work in the fluidized bed is preferred to minimize the problems associated with overheating hazards and distribution within the layer. The mode of operation in the fluidized bed allows you to add or remove the catalyst, if necessary for replacement or regeneration.

The following section provides details, including preferred variants of the present izobreteny is. However, it should be clear that, for a typical prior art can modify (to modify or adapt the various parameters without deviation from the scope of the present invention.

All catalysts were initially prepared on the basis of the disclosures of the claims provided in U.S. patent 4457905, the content of which is incorporated herein by reference. In this document these unmodified catalysts are referred to as MnaPOx/50%SiO2the catalysts.

The example for comparison

336,68 g of an aqueous solution of manganese nitrate concentration 51,3% was added to the reactor. 89.2 g of phosphoric acid concentration of 85% and 46,31 g of silica Sol Nalco 2327 concentration of 40% was introduced into the reactor with vigorous stirring. The temperature was raised to 103-105°C, and the reaction mixture was heated up until its volume has not decreased to about 200 ml This stage of evaporation is very essential for obtaining a catalyst of the desired density. The reaction mixture was cooled to room temperature and introduced into the resulting suspension additionally 262,56 g of silica Sol Nalco 2327. The resulting mass is milled for about 16 hours, dried and progulivali for 2 hours at a temperature of 935°C.

Mainly modified Mn-P catalysts, have the been created as well as modified catalysts, were made using the method of wet impregnation for the introduction of various metals such as Ca, K, Mo, Fe, and Zn from aqueous solutions of their soluble salts in the catalyst, previously dried at 200°C. For wet impregnation followed by annealing at two different temperatures of 850°C and 935°C for 2 hours in air.

Example 1

Modified zinc catalyst was obtained by the following procedure: 1 g of zinc nitrate, corresponding to the chemical formula Zn(NO3)2·6H2O, was dissolved in 9 ml of water. The solution was added to 20 g of dry catalyst material with stirring; the resulting material was dried at 110°C. the Dry material was divided into 2 parts. One part was annealed at 850°C for 2 hours. Another part was annealed at 935°C for 2 hours. The catalyst had the following composition: Mn1,25P1Zn0,046Ox/50%SiO2.

Example 2

Modified molybdenum catalyst was obtained by the following procedure: 10 g of (NH4)6Mo7O24was dissolved in 20 ml of water. The solution was added to 20 g of dry catalyst material with stirring; the resulting material was dried at 110°C. the Dry material was divided into 2 parts. One part was annealed at 850°C for 2 hours. Another part was annealed at 935°C for 2 hours. Ka is alistor had the following composition:

Mn1,25P1Mo0,81Ox/50%SiO2.

Example 3

Modified potassium catalyst was manufactured by the following method: of 0.53 g of potassium hydrofolate was dissolved in 10 ml of water. The solution was added to 20 g of dry catalyst material with stirring; the resulting material was dried at 110°C. the Dry material was divided into 2 parts. One part was annealed at 850°C for 2 hours. Another part was annealed at 935°C for 2 hours. The catalyst had the following composition:

Mn1,25P1Kbeing 0.036Ox/50%SiO2.

Example 4

Modified zinc catalyst was obtained by the following procedure: 2.7 g of zinc nitrate, corresponding to the chemical formula Zn(NO3)2·6H2O, was dissolved in 8 ml of water. The solution was added to 20 g of dry catalyst material with stirring; the resulting material was dried at 110°C. the Dry material was divided into 2 parts. One part was annealed at 850°C for 2 hours. Another part was annealed at 935°C for 2 hours. The catalyst had the following composition: Mn1,25P1Zn0,14Ox/50%SiO2.

Example 5

Modified calcium catalyst was obtained by the following procedure: 1 g of calcium nitrate, corresponding to the chemical formula CA(NO3)2·4H2Oh, rest rely in 8 ml of water. The solution was added to 20 g of dry catalyst material with stirring; the resulting material was dried at 110°C. the Dry material was divided into 2 parts. One part was annealed at 850°C for 2 hours. Another part was annealed at 935°C for 2 hours. The catalyst had the following composition:

Mn1,25P1Ca0,14Ox/50%SiO2.

Tests to determine the operational characteristics

All samples were tested in the oxidation of methanol in ammonia environment. All tests were performed in the reaction vessel of stainless steel 3/8" fluidized bed. The results of the validation of the operational characteristics are presented in table 2.

Chemical conversion of methanol was calculated using the following formula:

XCH3OH=1-[SN3HE]out/([CH3HE]out+[CO]out+[CO2]out+[HCN]out)×100%,

where [SN3HE]out, [CO]out, [CO2]out, [HCN]outconcentration of the reaction products in the eluate, expressed in volume percent.

Selectivity to HCN was calculated using the following formula:

SHCN=[HCN]out/([CO]out+[CO2]out+[HCN]out)×100%.

The output of cyanide (YHCN) was calculated using the following formula:

YHCN= (number of moles obtained [HCN]/the number is about moles [CH 3HE's] in the original product)×100%.

W/F (g·s/(ml at STP - standard temperature and pressure) refers to the contact time, where W is the weight of the catalyst; F - total volume submitted gases.

Table 2
The composition of the original product (mol%), W/F (g·s/ml at STP - standard temperature and pressure) and the results of the test characteristics
The temperature in the reactor, °CW/F
The contact time
NH3CH3HEO2Chemical transformation of CH3HE %The selectivity of HCN,%The release of HCN,%
The example for comparison, unmodified catalyst, the temperature of the annealing 935°C
4455,819,2117,5728,0498,582,481,1
4525,819,2117,57 of 99.181,881,1
4385,819,2117,5728,0498,482,280,9
Example 1, a catalyst, a modified Zn, the temperature of the annealing 935°C
438a 4.918,3316,5928,2096,5685,2583,15
418a 4.918,3316,5928,2093,6086,4582,65
428a 4.918,3316,5928,2097,0189,5886,88
448a 4.918,3316,59 28,2099,0589,0188,17
470a 4.918,3316,5928,2099,8693,4893,35
Example 1, a catalyst, a modified Zn, the annealing temperature of 850°C
438a 4.918,5616,6928,0699,64at 83.5483,27
418a 4.918,5616,6928,0699,0586,2685,44
428a 4.918,5616,6928,0699,6285,3084,97
Example 2, a catalyst, a modified MoE temperature annealing 935°C
4255,819,4818,0527,6499,681,581,1
4185,819,4818,0527,6499,581,481,0
Example 2, a catalyst, a modified Mo, the annealing temperature of 850°C
438a 3.87(Jn 19 : 2617,8528,1499,282,181,4
425a 3.87(Jn 19 : 2617,8528,14the 98.9of 83.482,5
Example 3, the catalyst modified By temperature annealing 935°C
4385,818,8217,45 28,5894,887,182,6
4455,818,8217,4528,5896,186,383,0
4525,818,8217,4528,5897,286,083,6
Example 4, a catalyst, a modified Zn, the temperature of the annealing 935°C
438a 4.918,4616,0928,3697,2189,9388,10
418a 4.918,4616,0928,3694,9391,4786,83
428a 4.918,4616,09 28,3697,8290,9388,79
448a 4.918,4616,0928,3699,0389,6689,01
458a 4.918,4616,0928,3699,6687,5287,28
438a 4.918,4616,0928,3698,6990,0489,13
Example 5 catalyst modified Sa temperature annealing 935°C
4505,818,1516,5126,8695,987,784,1

To enhance the performance of the catalyst described in U.S. patent 4457905, were introduced accelerators, K, CA, Mo, Zn and Fe. To talesfore, manufactured using K and Sa had the best selectivity to HCN, which led to increase by 2-3% compared to the unmodified catalyst. The catalyst-modified Mo, has a much higher activity than the unmodified catalyst, and to a certain initial amount of methanol will require a smaller amount of catalyst. The catalyst modified Zn, has a much higher activity and selectivity than the unmodified catalyst that allows you to use a smaller amount of catalyst for a certain number of the original product, maintaining a high chemical conversion of methanol and providing very high output HCN.

For industrial use it is very important to have almost complete chemical conversion of methanol. Increased activity of the modified Zn Mn-P catalyst is an advantage compared to the unmodified catalyst, since it allows to provide a higher concentration of methanol in the filing of the original product, in comparison with the concentration, which was disclosed in U.S. patent 4457905. In the present invention, all samples were tested without the use of steam, which is used to improve the selectivity with respect to HCN using namadi tirovannyh catalysts, as described in U.S. patent 4457905. No need to use steam to increase the output provides another advantage Mn-P catalyst in accordance with the present invention.

In contrast to previous catalysts modified Mn-P catalyst in accordance with the present invention can be used for a wider range of source products fed to the reactor, such as NITRILES, or mixtures of alcohols and NITRILES. When using as starting product propionitrile modified Fe-Mn-P catalyst provides much better features than the unmodified catalyst. The following experiment was conducted using propionitrile (PN) as a nitrile of the original product.

The sample using the nitrile of the original product

The original product consisting of methanol and propionitrile (PN), taken in the ratio of 50:50 by weight, was applied to the reactor together with the catalyst, modified with Fe, as described in U.S. patent 4457905. It was found that the mixture of methanol and PN, taken in the ratio of 50:50 by weight, converted into HCN with almost the same output as pure methanol, i.e. approximately 70-72%. Chemical transformation PN is almost 100%, except HCN-facing product contains CO, CO2and a small amount of impurities.

When COI is whether the PN as the original product was detected, that pure Mn-P catalyst hardly gives you the opportunity to get any amount of HCN from PN in the temperature range from 350 to 450°C, while the modified iron-Mn-P catalyst results in the release of HCN about 50% (calculated on the basis of C) even at 350°C.

Although the present invention is disclosed as a preferred variant embodiment, it should be understood that it is possible to make numerous additional modifications and variations in addition to this invention without departure from the scope of the present invention, as determined in accordance with the invention.

1. The method of ammonium oxidation in the environment of the original product in the form of alcohol or nitrile, or a mixture of alcohol and nitrile to cyanide, including the introduction referred to the original product with ammonia and oxygen in the reaction zone in the presence of the modified Mn-R-a catalyst having the following empirical formula:
MnaP1AbOx,
where a is one or more elements K, CA, Mo, Zn, Fe or mixtures thereof;
a = from 1 to 1.5; b = from 0.01 to 1.0 and x is the total number of oxygen atoms determined by the oxidation state of the elements present.

2. The method according to claim 1, wherein the catalyst is on a substrate.

3. The method according to claim 2, in which the substrate is chosen from the group consisting of TiO2, Al2O3The SiO 2.

4. The method according to claim 3, in which the substrate is SiO2.

5. The method according to claim 1, in which the mentioned source alcohol is methanol.

6. The method according to claim 1 in which the said oxygen is supplied as air.

7. The method according to claim 1, in which the mentioned source nitrile is propionitrile.

8. The method according to claim 7, in which a is Fe.

9. The method according to claim 1, in which the aforementioned modified Mn-R-a catalyst used in a fluidized bed of catalyst.

10. The oxidation catalyst in the ammonia environment, the source of the product in the form of alcohols, or NITRILES, or mixtures of alcohols and NITRILES to cyanide having the following empirical formula:
MnaP1AbOx,
where a is one or more elements K, CA, Mo, Zn, Fe or their combination;
a - 1 to 1.5; b = 0.01 to 1.0 and x is the total number of oxygen atoms determined by the oxidation state of the elements present.

11. The catalyst according to claim 10, in which the said catalyst is on a substrate.

12. The catalyst according to claim 11, in which the substrate is chosen from the group consisting of TiO2, Al2O3and SiO2.

13. The catalyst according to item 12, in which the substrate is SiO2.



 

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5 cl, 6 ex

FIELD: regeneration of free cyanide in waste technological solutions containing cyanides and heavy metals; non-ferrous metallurgical plants; gold mining and galvanic processes.

SUBSTANCE: proposed method consists in treatment of waste technological solutions by mineral acid under conditions excluding formation of gaseous hydrocyanic acid followed by separation of phases: solution of hydrocyanic acid and difficultly soluble compounds of elementary cyanides of metals by settling and/or filtration, leaching of clarified solution and re-use of solution of free cyanide thus obtained. Regeneration of free cyanide is carried out directly in solution being treated without conversion of hydrocyanic acid into gaseous phase.

EFFECT: repeated use of cyanide; reduced consumption of cyanide and fresh water; facilitated procedure; extraction of non-ferrous metals from solution in form of compact concentrate.

1 dwg, 2 ex

The invention relates to methods of producing hydrogen cyanide

The invention relates to a method of reducing leakage of ammonia and the corresponding reduction of ammonium sulfate and wastes derived from the unreacted ammonia in the production of Acrylonitrile direct oxidative ammonolysis of the unsaturated or saturated hydrocarbon, preferably propylene or propane, ammonia and oxygen in a reactor with a fluidized bed containing a catalyst of oxidative ammonolysis
The invention relates to the stabilization of the crude acetonitrile, in particular crude acetonitrile, obtained as a byproduct in the production of Acrylonitrile

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a hydrotreatment catalyst. Described is a method of producing a hydrotreatment catalyst which involves the following steps: a) at least one step for saturating a dried and/or annealed catalyst precursor containing at least one group VIII element and/or at least one group VIB element and an amorphous support using an impregnating solution consisting of at least one phosphorus-containing compound dissolved in at least one polar solvent with relative permittivity higher than 20; b) a step for maturation of said saturated catalyst precursor obtained at step a); wherein said maturation step is carried out at atmospheric pressure, at temperature ranging from ambient temperature to 60°C for maturation period of 12 to 340 hours; c) a step for drying without a subsequent step for annealing said catalyst precursor obtained at step b), wherein the drying step c) is carried out in a drying oven at atmospheric or low pressure and at temperature 50-200°C. Described is use of the catalyst obtained using the described method to carry out hydrofining and hydroconversion of hydrocarbon material.

EFFECT: high catalyst activity.

14 cl, 8 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.

EFFECT: increase of conversion degree of sulphur, microcarbon residue.

23 cl, 3 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: proposed catalyst is composed of 12.0-25.0% MoO3, 3.3-6.5% CoO, 0.5-1.0% P2O5, and Al2O3 to the balance. Catalyst preparation comprises one- or two-step impregnation of support with solution obtained by mixing solutions of ammonium paramolybdate, cobalt nitrate, phosphoric and citric acids taken at ratios P/Mo = 0.06-0.15 and citric acid monohydrate/Co = 1±0.1, or mixing solutions of ammonium paramolybdate and phosphoric acid at ratio P/Mo 0.06-0.15 and cobalt acetate followed by drying and calcination stages. Diesel fraction hydrodesulfurization process is carried out in presence of above-defined catalyst at 340-360°C and H2-to-feedstock ratio = 500.

EFFECT: intensified diesel fraction desulfurization.

7 cl, 2 tbl, 13 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.

EFFECT: intensified diesel fraction desulfurization.

9 cl, 3 tbl, 19 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting a mixture of carbon monoxide and hydrogen at increased temperature and pressure with a catalyst comprising manganese and cobalt on a carrier wherein cobalt, at least partially, presents as metal and catalyst comprises also inorganic phosphate in the amount at least 0.05 wt.-% as measure for elementary phosphorus relatively to the catalyst weight. Also, catalyst can comprise vanadium, zirconium, rhenium or ruthenium additionally. Method provides selectivity in formation (C5+)-hydrocarbons and decrease in formation of CO2.

EFFECT: improved preparing method.

7 cl, 1 tbl, 2 ex

The invention relates to new furifosmin formula I

< / BR>
where n denotes an integer of 1 or 2; R1denotes a hydrophilic group selected from the following groups: -SO2M, -SO3M, -CO2M, -PO3M, where M represents inorganic or organic cationic residue selected from a proton, cations, alkaline or alkaline earth metals, ammonium cations -- N(R)4where R denotes hydrogen or C1-C14alkyl, and the other cations are based on metals, salts with acids: fullsleeve, fullcarbon, fullsleeve or furylphosphonous soluble in water; m denotes an integer of 1; R2denotes a hydrophilic group,- SO2M, -SO3M, -CO2M, RHO3M, where M denotes hydrogen or an alkaline metal salt with the acid fullsleeve, fullcarbon, fullsleeve or fullfactorial soluble in water, R denotes an integer from 0 to 2

The invention relates to catalysts for deep oxidation of CO, hydrocarbons, soot, purification of vehicle exhaust and waste gases of industrial enterprises

The invention relates to a catalyst used for oxidation of ethylene to acetic acid, as well as to the way such oxidation using said catalyst

FIELD: chemistry.

SUBSTANCE: invention can be used in synthesis of organochloride compounds for reclamation of chlorine from waste hydrogen chloride. The components of the vanadium catalyst for oxidising hydrogen chloride to chlorine with molecular oxygen are vanadates of ammonium, potassium, sodium or lithium (2.5-10 wt % vanadium of the total weight of the catalyst), sulphates and hydroxides of potassium, sodium or lithium (1.2-21.6 wt % alkali metals in form of sulphates and hydroxides, of the total weight of the catalyst) and phosphoric acid (2-35 wt % of the total weight of the catalyst), which are deposited on silica gel or aluminium oxide (the rest - up to 100 wt %). The silica gel or aluminium oxide has specific surface area of 80-800 m2/g, pore volume of 0.3-4.5 ml/g and particle size of 0.1-20 mm.

EFFECT: invention increases stability of the catalyst 2,5-33-fold and widens the operating temperature range of the process to 450°C.

12 ex

FIELD: process engineering.

SUBSTANCE: invention relates to production of liquid fluid. Liquid fuel production by wax hydrocarbons hydrocracking in Fischer-Tropsh synthesis comprises bringing paraffin hydrocarbons in contact with catalyst in the presence of hydrogen. Note here that said catalyst comprises carrier including crystalline aluminosilicate and amorphous harsh acid, and at least one element selected from the VIII group of periodic table retained on said carrier and additionally containing phosphorus.

EFFECT: higher yield of medium distillate.

5 cl, 1 tbl, 1 dwg, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to promoter catalysts on a combined zeolite/aluminosilicate substrate with low content of macropores and to methods of hydrocracking/hydroconversion and hydrofining, in which said catalysts are used. The catalyst contains at least one hydrogenating-dehydrogenating element, selected from a group comprising group VIB and group VIII elements, a promoter element in a controlled amount, selected from phosphorus oxide, and a substrate based on zeolite Y, defined by constant a of the unit cell of the crystal lattice, ranging from 24.40·10-10 m to 24.15·10-10 m, and based on aluminosilicate, containing silicon dioxide (SiO2) in amount exceeding 5 wt % and less than or equal to 95 wt %. The catalyst has the following characteristics: average pore diametre, total pore volume, BET specific surface area, volume of pores of different diametre, characterised by X-ray diffraction pattern and packing degree of the catalyst.

EFFECT: catalyst provides for suitable selectivity of middle distillates, ie fractions with initial boiling point of at least 150°C and final boiling point which reaches initial boiling point of residue, for example below 340°C or 370°C.

28 cl, 4 tbl, 21 ex

FIELD: chemistry.

SUBSTANCE: catalytically active amorphous porous solid substance is used for catalysed with acids industrial chemical processes such as, for example alkylation, isomerisation, hydrogenation-dehydrogenation, which include mixed silicon, aluminium and phosphorus oxide. Ratio Si/Al is from 20 to 250, ratio P/AI is from 0.1 to 3.5. General pore size is from 0.5 to 2.0 ml/g, average pore diameter is from 3 to 40 nm, and specific surface area is from 200 to 1000 m2/g. Method of its obtaining includes : water mixture preparation, which includes tetraalkylammonium hydroxide, hydrolysed aluminium compound, hydrolysed silicon compound and oxygen-containing phosphorus compound in such proportions, that atomic ratio Si/Al is from 10 to 250, and ratio P/Al is from 0.1 to 3.5, and amount of water, sufficient for solution and hydrolysis of said compounds. Heating of this mixture in alkaline medium, preferably supporting pH value higher than 10, and in such way that mass-exchange with surrounding environment in fact does not take place, to achieve gel formation, and its further drying and calcination. Invention also belongs to catalytically active solid composition and method of its preparation, which includes mixture formation, which contains from 30 to 99% wt, of said amorphous substance and from 70 to 1 % wt of inert inorganic binding agent, extrusion , drying and calcination of obtained mixture.

EFFECT: increased activity and selectivity in comparison with traditional amorphous alumosilicate gels.

27 cl, 20 ex, 5 tbl

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