The method of obtaining 1,4-butandiol

 

(57) Abstract:

The invention relates to chemical technology, more specifically to an improved process for the preparation of the catalyst and synthesis of 1,4-butandiol from acetylene and formaldehyde. It is proposed to obtain a catalyst for the synthesis of 1,4-butandiol on the basis of the kaolin, which is mixed with water in the ratio of 3.5 : 1, molded from the obtained paste extrudates, dried at 120-160°C, calcined at 900-1100oWith and cool. From the received carrier to prepare the catalyst, impregnating it with an aqueous solution of nitrate salts of metals containing in terms of metal, g/DM3: copper 200-230, Nickel 2-12 and/or bismuth 70-90, and calcined impregnating the carrier with 360-480°C. as the carrier also use kaolin media obtained after regeneration of the copper-Nickel-chromium catalyst for the hydrogenation of 1,4 - butynediol in 1,4-butanediol. The prepared catalyst having the composition, wt.%, in terms of metal: Cu 3,0-7,0; Ni 0,05-0,30 and/or Bi 1,0-3,0; kaolin to 100, activate a 37% aqueous solution of formaldehyde, barbotine gaseous acetylene by heating. Synthesis of 1,4-butandiol carried out on the activated catalyst at a temperature of 80-120oC, a pressure of 0.1-1.0 MPa, flow rate of Podaca relates to the field of organic chemistry, more specifically to methods of producing acetylene glycols, rather 1,4-butandiol from acetylene and formaldehyde in the catalysts of acetylene copper on solid media.

A method of obtaining 1,4-butandiol [1] (Pat. USA N4143231, 06.03.79, C 07 C 33/04), according to which the reaction of condensation of acetylene and formaldehyde is carried out at 90oC for 8 hours in the presence of suspended copper-bismuth catalyst based on synthetic malachite.

The catalyst is prepared from solutions of the nitrates of copper and bismuth mixed with sodium carbonate solution, resulting in precipitation of synthetic malachite with a particle size of 15-25 microns, containing 35% of bismuth.

Activation of the catalyst is carried out by bubbling nitrogen-acetylene mixture through a suspension of suspension of synthetic malachite in formalin solution.

Synthesis is carried out under conditions of ideal mixing reactor, through which the suspension is loaded activated catalyst in 15% formalin solution bubbled acetylene for 8 hours at a temperature of 90-95oC. the Concentration of formalin support not lower than 10 wt.%, adding fresh 37% formalin, pH of the medium support in the range of 6.0 to 6.2 by addition of a solution of bisadora is 0.7 g/hour of the absorbed acetylene per 1 g of copper in the catalyst, mileage catalyst 205 hours.

A similar method of obtaining 1,4-butanediol on a suspended catalyst based on synthetic malachite with the addition of bismuth and silica gel described in [2] (U.S. Pat. USA N 4584418, 1986, 15.03.85,, C 07 C 29/00 C 07 C 33/046).

According to the method, synthetic malachite precipitated in the presence of bismuth nitrate and sodium silicate. Get sinter synthetic malachite diameter of 6 μm, containing 0,67% silicic acid and 3% bismuth.

The suspension of catalyst activated in a solution of 47% formalin, barbotine nitrogen-acetylene mixture. Synthesis of 1,4-butandiol carried out at 90oC for 2 hours, maintaining the pH of the solution in the range of 5.0 to 6.5 solution of soda. Conversion of formaldehyde reaches 95%.

According to the method of [3] (Ed. St. USSR N 191491, C 07 C 33/04, BI 1967, 44) used suspended copper-bismuth on the pumice catalyst with a particle size less than 0.25 mm, the Catalyst is prepared by mixing powder of pumice with aqueous solutions of the nitrates of copper and bismuth, the evaporation mass to dryness, calcining the powder at 450oC. the resulting catalyst containing copper 30%, bismuth, 7%, activate, barbotine acetylene through the suspension of catalyst in formaldehyde at a temperature of 70-90oP> 37% aqueous formaldehyde solution, heated to 90oC and 4 hours bubbled acetylene until the residual content of formaldehyde of 0.8%. The output of butandiol 95.3% on the formalin.

In the method [4] (U.S. Pat. Germany N 2206693 from 12.02.72,, C 07 C 33/04) describes the obtaining of 1,4-butandiol in a cascade of four reactors at a temperature of 95oC and a pressure of 0.14 MPa. As catalyst, use dispersed silica gel containing acetylenic metals, wt.%: Cu - 50; Bi - 14; Co - 2 in terms of metal. The yield of 1,4 - butandiol up to 98%.

In the patent [5] (U.S. Pat. Poland N 117553 from 04.11.78,, C 07 C 33/046) proposed to use a catalyst in which the carrier is talc. The source powder is poured a solution of nitrate of copper, bismuth, iron, Nickel, evaporated, dried at 300oC and calcined at 500oC. the Obtained catalyst mass activate acetylene, barbotine it through a suspension of powder in a solution of formalin. Synthesis of 1,4-butandiol carried out at 92oC, maintaining the pH of the solution in the range of 6-9. Exit 1,4-diol 196 g/kg of catalyst per hour.

The disadvantages of these methods should include technological difficulties in the use of suspended catalysts (difficulties in separation from catalyzate abrasive wear S="ptx2">

The above disadvantage is suspended catalyst is a serious technical obstacle for the industrial use of such catalysts.

On an industrial scale often use heterogeneous catalysts in granular form, with the notion of granules includes any form and method of preparation of the catalyst, for example, tablets, extrudates, beads, etc. that allows you to place the catalyst in the reaction apparatus in the form of a fixed layer.

In method [6] (U.S. Pat. UK N 802794, 1958 and Germany N 1072985, 08.10.58,, CA 1959, 4140 C) describes the obtaining of 1,4-butandiol in the flow reactor, the catalyst is copper-bismuth on magnesium silicate (CuO - 15%; Bi2O3- 3%). The process is conducted at 80 - 110oC and a pressure of 0.12 MPa. The feed rate of acetylene 130 cubic feet/hour, formalin (37%) of 7 Gal/h at 19 cubic feet/catalyst. Get to 7.7 Gal/hour of product, which is neutralized to pH 5 and dispersed. Exit 1,4-diol 78% acetylene and 90% in the formalin.

At the Novocherkassk plant of synthetic products [7] (Constant Technological regulation No. 52, Novocherkassk, 1979, page 14-18) operates an industrial unit for obtaining 1,4-butandiol condensation of formaldehyde and acetylene. The process of ASU who are hydrothermally treated silica gel carrier for the catalyst of synthetic alcohol, on which the impregnation is applied active metals copper and bismuth in a mass ratio of 4.5:1. The catalyst has the following composition, wt.%: CuO - 14-16; Bi2O3- 3-4, the rest hydrothermally treated silica (silica gel carrier of the catalyst for the synthesis of alcohol).

The specified catalyst is characterized by low activity, low service life due to low mechanical stability in aqueous medium under the conditions of synthesis, which leads to fragmentation and ablation of the catalyst in the mass of the reaction solution, the danger of explosion in the separation of suspensions carry out the catalyst from the reaction solution.

The disadvantages of the processes described in method [6] and the regulations on production [7], are mainly in the shortcomings of the used catalysts - high concentration of active metals, low strength and, as a consequence, the short life of the catalysts and the low selectivity of the process.

The closest technical solution is the method of preparation of the catalyst and obtain 1,4 - butandiol described in [8] (U.S. Pat. USA N 2840618, from 24.06.1958,, R j 1959, 75738 P). According to the method prototype catalyst is prepared by impregnation of kaolin media solution nor esenich metals. Original kaolin carrier is prepared from a powder of kaolin composition: Al2O32SiO22H2O by mixing it with a 30% aqueous solution of polymer, such as salts of polyacrylic, polymannuronate and polygalacturonic acids, methylcellulose, or, best of all, with a solution polivinilovogo ether, in a weight ratio of carrier:a solution of 2:1 to obtain the consistency of putty. The mixture is forced through a Spinneret to obtain extrudates, which are dried at 80-90oC, and then calcined in a stream of air for 5 hours at a temperature of 800-850oC. these conditions result In the burning of the organic binder and the formation of the original kaolin structure of montmorillonite. Then continue roasting at a temperature of 1080oC to give the catalyst structure of mullite 3Al2O32SiO2. After cooling, the resulting carrier is impregnated with an aqueous solution of nitrates of copper and bismuth, dried for 42 hours at 80oC, calcined 36 hours at 500oC, cooled and activate the 12% solution of formaldehyde for 30 minutes while bubbling acetylene. The prepared catalyst containing, calculated on the metal, wt. %: Cu - 8.4%, and Bi - 6,4%, the rest is kaolin, used in the synthesis of 1,4-butandiol.

The purpose of the present invention is to develop new technologies for media and based on a more efficient catalyst and increase, at the expense of its application, the efficiency of the production of 1,4-butandiol.

To achieve this goal the catalyst for the synthesis of 1,4-butandiol prepared on the basis of kaolin by mixing it with water, molding the resulting paste through a Spinneret into extrudates, drying, calcination at 900-1100oC, cooling, impregnation with an aqueous solution of nitrates of copper, Nickel and/or bismuth and calcination in a stream of air at a temperature of 360-480oC. the Finished catalyst activated in 37% aqueous solution of technical formaldehyde when heated and the gaseous acetylene. On the activated catalyst to carry out the synthesis of 1,4-butandiol at a temperature of 80-120oC and a pressure of 0.1-1.0 MPa, feeding him the raw material mixture consisting of an aqueous solution of formaldehyde and acetylene. As a carrier for catalyst for copper-Nickel-chrome on kaolin (MNH-R), used in the process of hydrogenation of 1,4-butynediol in 1,4-butanediol (see "Method of regeneration of spent Nickel-containing hydrogenation catalyst", U.S. Pat. RF N 2100071 from 27.12.97, on request N 96103933 from 05.03.96 year).

In accordance with the proposed method, the process of preparation of the catalyst and obtaining 1,4-butandiol is as follows.

Original kaolin powder is mixed with water in a mass ratio of 3.5: 1. From the resulting pasty mass is formed extrudates, dried in a stream of air at 120-160oC for 12 hours and then calcined in a stream of flue gases at a temperature of 900-1100oC for 14 hours. In the annealing process of heating and subsequent cooling media are at a rate not exceeding 30oC per hour.

The cooled media is impregnated at a temperature of 60oC for 30 minutes in an aqueous solution of nitrate salts of copper, Nickel and/or bismuth, taken in the ratio of carrier: solution 1:1,1. The impregnated carrier is calcined in air flow at a temperature of 360-480oC. the Rate of heating and cooling of the catalyst in the process of calcination is not more than 30oC per hour.

Impregnating a solution of nitrate salts of copper, Nickel and/or bismuth has a policy component, in terms of metal, g/DM3:

Cu - 200 - 230; Ni - 2 - 12; and/or Bi - 70 - 90.

Activatable kaolin catalyst has the following characteristics:

bulk density, kg/DM3- 0,75 - 0,80,

composition, wt.%, in terms of metal:

Cu - 3,0 - 7,0; Ni - 0,05 - 0,30; and/or Bi - 1,0 - 3,0.

Prepared as described catalyst loaded into the reactor column type and hold activation:

heat the catalyst up to 96oC with a circulating solution of 37% technical formalin supplied with a bulk velocity of 0.1-0.5 h-1and the gaseous acetylene with a bulk velocity 10-60 h-1.

After activation serves raw ingredients: 10% aqueous formalin and gaseous acetylene, supporting the following conditions process: volumetric feed rate of formalin 0.1 to 0.5 h-1, acetylene 10-60 h-1the pressure in the reactor of 0.1 to 1.0 MPa, the temperature in the reaction zone in the range of 80-120oC.

The reaction products drossellied to atmospheric pressure, separating the gaseous products, liquid is neutralized with alkali to pH 8-9, and then distil them in a known manner from light impurities and receive commercial 1,4-butandiol.

the one kaolin with water in the ratio of 3.5:1;

- drying the molded carrier in a stream of air at 120-160oC;

the calcination of the dry molded carrier at a temperature of 900-1100oC in a stream of flue gas;

- impregnation of the finished carrier with a solution of nitrate salts of the following composition, g/DM3: copper - 200 - 230; Nickel - 2 - 12; and/or bismuth - 70 - 90 followed by calcining in a stream of air at 360-480oC.

A distinctive feature of the proposed method to obtain 1,4-butandiol is the use of a catalyst having the composition, wt.%, in terms of metal:

Cu - 3,0 - 7,0; Ni - 0,05 - 0,30 and/or Bi - 1,0 - 3,0; kaolin to 100.

An additional distinctive feature of the proposed method is the possibility of using kaolin media obtained during the regeneration of the copper-Nickel-chromium catalyst for the hydrogenation of 1,4-butynediol. The regenerated carrier impregnated with solutions of metal nitrates and processed in the described manner.

The invention, in the opinion of the applicants meet the conditions of patentability. It is new, because the applicants do not know the sources that provide the conditions for preparation of the catalyst synthesis of 1,4-butynediol containing active ingredients in the claimed limits of composition, population, or use kaolin media obtained during the regeneration of the copper-Nickel-chromium catalyst for the hydrogenation of 1,4-butynediol.

The present invention involves an inventive step, since it is not clear from the prior art. First of all, because in the literature there are no data for the preparation of copper-Nickel-bismuth or copper-bismuth-based catalyst kaolin and conditions for the heat treatment of the carrier and catalyst for their formation, similar to those suggested by the present invention.

The present invention is industrially, because its implementation does not require any special equipment or inaccessible and expensive raw materials.

The method is illustrated by the following examples.

Example 1

Original kaolin powder in the amount of 2100 g and 600 cm3water is mixed for 1.0 hour, the resulting paste is molded in the form of extrudates with a diameter of 4 mm and a length of 4 to 15 mm extrudates are dried in a drying Cabinet at a temperature of 140oC for 12 hours, then overload them in a tube furnace for calcination. Warming up of the catalyst are hot flue gases produced by burning natural mperature 1070oC make the shutter 14 hours, then cooled calcined extrudates, diluting the combustion gases with air so that the cooling rate was 30oC.

Received kaolin media has the following characteristics:

bulk density, kg/DM3- 0,75; moisture absorption, DM3/DM3- 0,25.

Media in number 2700 cm is placed in an impregnating bath, there is poured 3000 cm3solution of the nitrates of the metals of the following composition, g/DM3in terms of metal: Cu - 213; Ni - 8,8; Bi - 77. The solution temperature 60oC, time of impregnation 30 minutes. The impregnated carrier is removed from solution, is loaded into progulochnuju oven, heated with hot air at a speed of 30oC per hour up to 400oC and kept at this temperature for 14 hours, then cooled and discharged.

The finished catalyst has the following characteristics:

bulk density, kg/DM3- 0,77

composition, wt.%, including:

copper - 5,85; Nickel 0,25; bismuth - 2,07; the rest is kaolin.

The catalyst in quantities of 1000 cm3placed in the synthesis reactor, pour it 1200 cm337% solution of formaldehyde and serves gaseous acetylene with a bulk velocity 20 h-1. Activate the AI set operating temperature - 95oC. raw materials: formaldehyde having a concentration of formaldehyde of 10.1 wt.%, served in a reactor with a volume rate of 0.2 h-1, acetylene served with a bulk velocity of 20 h-1.

The balance of experience (table. 1)

Analysis of the reaction products by gas chromatography showed that the conversion of formaldehyde is 86.6% with a selectivity of turning it in 1,4-butandiol to 84.6 mol.%.

The catalyst activity was evaluated by specific productivity (P) of the catalyst, calculated from the values obtained production of 1,4-butandiol per hour, referred to the unit volume of the catalyst:

P = G/Vcat,

G = Vff %f K S 86/2 30 1000

VfY= VcatF, or

P = VcatF f %f 86 / Vcat60000 kg/m3hour, where

P - capacity, kg/m3hour;

G - production of 1,4-butandiol, kg/h;

Vcat- the volume of the loaded catalyst, m3;

Vf- the amount of the missed solution of formaldehyde, m3per hour;

f is the density of the solution of formaldehyde, 1.0 kg/DM3< / BR>
%p - formaldehyde content in the raw material solution, wt.%;

F is the volumetric feed rate of solution of formaldehyde, h-1;

K - conversion of formaldehyde is respectively, 1,4-butandiol and formaldehyde;

2 - stoichiometric coefficient of discharge of formaldehyde;

1000 is the conversion factor dimension of productivity in kg of 1,4-butandiol per hour with 1 m3a catalyst.

After the transformation formula takes the form:

N = 1,433 10-3F %f To S kg/m3hour

N = 1,433 10-30,2 10,1 86,6 84,6 = 21,2 kg/m3hour

The results of example 1 and subsequent examples are shown in summary table 1.

Example 2

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the drying molded pulp was carried out at a temperature of 120oC and calcining at a temperature of flue gases 900oC.

The resulting catalyst composition, wt.% metal: Cu - 6,21; Ni - 0,27; Bi - 2,38; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 87,4% with a selectivity of turning it in 1,4-butandiol 86,2 mol.%. The performance of the catalyst is 21,8 kg/m3hour.

Example 3

Preparation of a catalyst based on kaolin was carried out under the conditions described in which when the temperature of the flue gases 1100oC.

The resulting catalyst composition, wt.%, metal: Cu - 4,35; Ni - 0,17; Bi - 1,72; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is of 89.1% with a selectivity of turning it in 1,4-butandiol to 86.4 mol.%. The performance of the catalyst is 22.3 kg/m3hour.

Example 4

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the drying molded pulp was carried out at a temperature of 100oC and calcining at a temperature of flue gases 800oC.

The resulting catalyst composition, wt.%, metal: Cu - 2,1; Ni - 0,15; Bi-1,3; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde or 65.3%, with selectivity turning it into 1,4-butandiol to 47.4 mol.%. The performance of the catalyst is 9.0 kg/m3hour.

Example 5

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the drying molded m>The resulting catalyst composition, wt.%, metal: Cu - 5,3; Ni - 0,2; Bi - 2,0; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 61,7% with selectivity turning it into 1,4-butandiol 79,4 mol.%. The performance of the catalyst is 14.2 kg/m3hour.

Example 6

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the ratio of kaolin: water was 3.3: 1.

The resulting catalyst composition, wt.%, metal: Cu - 5,31; Ni - 0,22; Bi - 1,98; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 82,7% with selectivity turning it into 1,4-butandiol 73,1 mol.%. The performance of the catalyst is 17.5 kg/m3hour.

Example 7

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the ratio of kaolin: water was 3.7:1.

The resulting catalyst composition, wt.%, metal: Cu - 4,

Analysis of the reaction products showed that the conversion of formaldehyde is 77,1% with a selectivity of turning it in 1,4-butandiol 84,9% mol. The performance of the catalyst is to 18.9 kg/m3hour.

Example 8

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the impregnating solution had the composition, g/DM3: copper - 200, Nickel - 2,0, bismuth 70.

The resulting catalyst composition, wt.%, metal: Cu - 3,0; Ni - 0,05; Bi - 1,0; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 87,1% with selectivity turning it into 1,4-butandiol 85,8 mol.%. The performance of the catalyst is 21.6 kg/m3hour.

Example 9

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the impregnating solution had the composition, g/DM3: copper - 230, Nickel - 12, bismuth - 90.

The resulting catalyst composition, wt.%, metal: Cu - 7,0; Ni - 0,30: Bi - 3,0; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Example 10

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the impregnating solution had the composition, g/DM3: copper - 190, Ni - 1, bismuth - 60.

The resulting catalyst composition, wt.%, metal: Cu - 2,85; Ni - 0,02; Bi - 0,9; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 67.3% with a selectivity of turning it in 1,4-butandiol 77,4 mol.%. The performance of the catalyst is 15.1 kg/m3hour.

Example 11

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the impregnating solution had the composition, g/DM3: copper - 250, Nickel - 16, bismuth - 100.

The resulting catalyst composition, wt.%, metal: Cu - 7,4; Ni - 0,45: Bi - 4,1; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 94,1% with a selectivity of turning it in 1,4-bulindi is giving catalyst based on kaolin was carried out under the conditions given in example 1, except that the temperature of calcining the impregnated carrier is 360oC. the resulting catalyst composition, wt.%, metal: Cu - 5,85; Ni - 0,25; Bi - 2,07; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 92,2% with a selectivity of turning it in 1,4-butandiol of 60.8 mol.%. The performance of the catalyst is 16.2 kg/m3hour.

Example 13

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the temperature of calcining the impregnated carrier is 480oC.

The resulting catalyst composition, wt.%, metal: Cu - 5,85; Ni - 0,25; Bi - 2,07; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 61,7% with selectivity turning it into 1,4-butandiol 74,4 mol.%. The performance of the catalyst is 13.3 kg/m3hour.

Example 14

Preparation of a catalyst based on kaolin was carried out under the conditions described in the example is the result of the catalyst composition, wt.%, metal: Cu - 5,85; Ni - 0,25; Bi - 2,07; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 48.8% with a selectivity of turning it in 1,4-butandiol of 62.3 mol.%. The performance of the catalyst is 8.8 kg/m3hour.

Example 15

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the temperature of calcining the impregnated carrier is 520oC.

The resulting catalyst composition, wt.%, metal: Cu - 5,85; Ni - 0,25; Bi - 2,07; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 73,8% with a selectivity of turning it in 1,4-butandiol 78,1 mol.%. The performance of the catalyst is 16.7 kg/m3hour.

Example 16

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1.

Testing of the catalyst was performed in the conditions of example 1, except that the temperature of synthesis is 80oC, volume korostelina is 88,3% with selectivity turning it into 1,4-butandiol 82,4 mol.%. The performance of the catalyst is 10.5 kg/m3hour.

Example 17

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1.

Testing of the catalyst was performed in the conditions of example 1, except that the temperature of synthesis is 120oC, a pressure of 1.0 MPa, the space velocity of the feed formalin mixture of 0.5 h-1and the volumetric feed rate of acetylene 60 h-1.

Analysis of the reaction products showed that the conversion of formaldehyde is 87,7% with a selectivity of turning it in 1,4-butandiol 78,9 mol.%. The performance of the catalyst is 50,1 kg/m3hour.

Example 18

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1.

Testing of the catalyst was performed in the conditions of example 1, except that the pressure in the synthesis was 0.1 MPa, the volumetric feed rate of acetylene 70 h-1.

Analysis of the reaction products showed that the conversion of formaldehyde is of 83.4% with a selectivity of turning it in 1,4-butandiol of 84.3 mol.%. The performance of the catalyst is 20.4 kg/m3hour.

Example 19

Photofinisher conducted under the conditions of example 1, except that the temperature of synthesis was 70oC.

Analysis of the reaction products showed that the conversion of formaldehyde is 63,4% with selectivity turning it into 1,4-butandiol 82,3 mol.%. The performance of the catalyst is 15.1 kg/m3hour.

Example 20

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1.

Testing of the catalyst was performed in the conditions of example 1, except that the temperature of synthesis was 130oC, the volumetric feed rate of formaldehyde mixture of 0.5 h-1, acetylene - 60 h-1.

Analysis of the reaction products showed that the conversion of formaldehyde is 88,1% with selectivity turning it into 1,4-butandiol 79,9 mol.%. The performance of the catalyst is 51,0 kg/m3hour.

Example 21

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1.

Testing of the catalyst was performed in the conditions of example 1, except that the amount of the feeding device acetyl 70 h-1.

Analysis of the reaction products showed that the conversion of formaldehyde is 87,0% when the selective behaviour is CLASS="ptx2">

Example 22

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1.

Testing of the catalyst was performed in the conditions of example 1, except that the volumetric rate of acetyl is 5 h-1.

Analysis of the reaction products showed that the conversion of formaldehyde is 69.7% with a selectivity of turning it in 1,4-butandiol 82,1 mol.%. The performance of the catalyst is 16.6 kg/m3hour.

Example 23

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the impregnating solution had the composition, g/DM3: copper - 215,2; bismuth - 78,3.

The resulting catalyst composition, wt.%, metal: Cu - 5,91; Bi - 2,11; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is to 85.5% at a selectivity of turning it in 1,4-butandiol to 87.1 mol.%. The performance of the catalyst is 21.6 kg/m3hour.

Example 24

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that the erali copper-Nickel-chrome catalyst contain Nickel in the amount of 0.13 wt.%, in terms of metal.

The resulting catalyst composition, wt.%, metal: Cu - 5,33; Ni - 0,13; Bi - 0,13; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 82,7% with selectivity turning it into 1,4-butandiol 86,6 mol.%. The performance of the catalyst is 20.7 kg/m3hour.

Example 25

Preparation of a catalyst based on kaolin was carried out under the conditions described in example 1, except that as the carrier for impregnation used regenerated kaolin media obtained after regeneration of the copper-Nickel-chrome catalyst containing Nickel, in the amount of 0.25 wt.%, in terms of metal.

The resulting catalyst composition, wt.%, metal: Cu - 6,25: Ni -0,25; Bi - 2,17; the rest is kaolin.

Testing of the catalyst was performed in the conditions of example 1.

Analysis of the reaction products showed that the conversion of formaldehyde is 89.2% with a selectivity of turning it in 1,4-butandiol to 87.1 mol.%. Catalyst productivity status is Yes and acetylene in the presence of pre-activated copper-bismuth on the kaolin catalyst, characterized in that the interaction is carried out at a temperature of 80 - 120oC and a pressure of 0.1 - 1.0 MPa in the volumetric feed rate of solution of formaldehyde of 0.1 - 0.5 h-1and acetylene 10 - 60 h-1in the presence of a catalyst of copper-bismuth on the kaolin, optionally containing a promoting additive Nickel and having a composition, wt.%, in terms of metal: Cu 3,0 - 7,0; Ni 0,05 - 0,30, and/or Bi 1,0 - 3,0, kaolin up to 100.

2. The preparation method of catalyst for the synthesis of 1,4-butandiol, including the preparation of a carrier by mixing the original kaolin powder in the presence of water, forming, drying, calcining, cooling and impregnation of the received carrier with aqueous solutions of nitrate salts of copper and bismuth, followed by calcining the impregnated carrier, characterized in that the starting kaolin is mixed with water in the ratio of 3.5 : 1, form the media and dry it at 120 - 160oC, calcined at 900 - 1100oC, cooled and impregnated with a solution of nitrate salts containing, calculated on the metal: copper 200 - 230 g/DM3; Nickel 2 - 12 g/DM3and/or bismuth 70 - 90 g/DM3and calcined impregnated carrier with 360 - 480oWith obtaining a catalyst of the following composition, wt. % in terms of metal: Cu 3,0 - 7,0; N catalyst for the synthesis of 1,4-butandiol use kaolin media obtained during the regeneration of the copper-Nickel-chromium catalyst for the hydrogenation of 1,4-butynediol in 1,4-butanediol.

 

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The invention relates to chemical technology, more specifically, to improved method of separation of acetylene from waste gases for 1,4-butandiol (1,4-BID) on the basis of acetylene and formaldehyde

The invention relates to unsaturated alcohols, in particular, to a method for primary alkyldiethanolamine alcohols of General formula

R-CC-CC-CH2OH

where R is methyl, ethyl, n-propyl and ISO-propyl, which may find application in thin organic synthesis, in particular in obtaining natural compounds: sex pheromones, prostaglandins, etc

The invention relates to a method for producing a catalyst containing a porous carrier and deposited thereon a catalytically active metal

The invention relates to catalytic chemistry, in particular to catalysts for the synthesis of dichloroethane oxychloination ethylene

The invention relates to methods for preparing catalysts for dehydrogenation of paraffin hydrocarbons, in particular for the dehydrogenation of C2-C5paraffins to the corresponding olefins

The invention relates to catalytic materials

The invention relates to catalytic chemistry, in particular to the preparation of catalysts for Hydrotreating of crude oil, and can be used in the refining industry

The invention relates to catalytic chemistry, in particular to methods of producing catalysts for neutralization of exhaust gases of internal combustion engines

The invention relates to methods of producing and catalysts for purification of exhaust gases of internal combustion engines
The invention relates to sorption technique and can be used for air purification from toxic impurities in the means of respiratory protection, industrial adsorbers, etc

The invention relates to catalytic compositions for the purification of terephthalic acid based on metals of group VIII, methods for their preparation and to a process for purifying terephthalic acid suitable in the future for the synthesis of polyester polymers and copolymers used in the production of textile fibers

The invention relates to the production of heterogeneous catalysts for liquid-phase oxidation of sulfur compounds (sulfur dioxides, verouderde, mercaptans) and can be used for purification of gas emissions and wastewater, energy, refining, petrochemical, chemical and pulp and paper industries

FIELD: chemistry.

SUBSTANCE: claimed invention relates to catalysts of hydration, method of their production and use for hydration such as selective hydration of acetylene admixtures in non-purified olefinic and diolefiniuc flows. Described is a selective catalyst of hydration for selective hydration of acetylene admixtures in non-purified olefinic and diolefinic flows, containing only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, applied on carrier, which is alumunium oxide with the following physical characteristics: BET surface area from 30 to approximately 100 m2/g, total volume of pores on nitrogen from 0.4 to approximately 0.9 cm3/g and the average pore diameter from approximately 110 to 450 Å , where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Described are the method of catalyst production, which includes impregnation of carrier represented by aluminium oxide and having the aforesaid physical characteristics, with soluble salts of only nickel or nickel and one or more elements chosen from the group consisting of Cu, Re, Pd, Zn, Mg, Mo, Ca and Bi, from one or more solutions, obtaining impregnated carrier, where the said catalyst contains from approximately 4 to approximately 20 weight % of nickel. Also described is the method of selective hydration of acetylene compounds, which includes contact of original raw material containing acetylene compounds and other unsaturated compounds, with the described above catalyst.

EFFECT: increased degree of 1,3-butadien extraction with full or nearly full conversion of C4-acetylenes.

25 cl, 1 dwg, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: description is given of a catalyst for converting ammonia to nitrogen (II) oxide with a block cellular structure, with the shape of a rectangular prism or oblique prism with obliquity of 0-45°, coefficient of thermal expansion in the interval 10-7-10-5 K-1 in the temperature range of 900°C, based on mixed oxides with general formula: xMe1O·yMe2O·(1-x-y)(2MgO·(2-z)Al2O3·(5+z)SiO2), where: x=0.03-0.25; y=0.01-0.1; z=0-2, Me1 - is an active component; Me2 - is a structural promoter. Described also is a method of catalytic conversion of ammonia, which involves passing a reaction gaseous mixture, containing ammonia and an oxygen containing gas, through a two-stage catalyst system, made using different methods, including in a set with trapping platinoid gauze and/or inert packing. The proposed catalyst is used in the second stage.

EFFECT: catalyst has high activity, selectivity and resistance to thermo-cycles when used in a two-stage system.

6 cl, 3 tbl, 13 ex

FIELD: chemistry.

SUBSTANCE: invention relates to regeneration of spent metal-containing catalysts for organic synthesis. Described is a method of regenerating metal oxide industrial catalysts for organic synthesis, comprising a support with oxides of Cu and Bi or Cu, Ni and Cr, the method involving treatment of the spent catalyst with salicylalaniline solution in dimethyl formamide with concentration between 0.1 and 0.5 mol, filtration of the solution of the complex compound, which is adsorbed directly on the cleaned support which is silica gel or zeolite obtained after filtration, and the obtained adsorbent undergoes thermal decomposition on the surface of the support at temperature 150-200°C.

EFFECT: described catalyst regeneration method enables multiple regenerations, lowers power consumption of the regeneration process while simplifying the process and without aggressive and toxic media.

2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a photocatalyst based on bismuthate of an alkali-earth metal and to a method for photocatalytic treatment of water from organic contaminants. Method of producing a photocatalyst involves dissolving bismuth nitrate and alkali-earth metal nitrate in a solvent, wherein solvent is an aqueous solution of polyatomic alcohol, containing at least five carbon atoms, with subsequent annealing of precursor at 550-650 °C to produce nanoparticles of amorphous bismuthate of alkali-earth metal of non-stoichiometric composition with degree of oxidation not equal to two. Prior to annealing, precursor is evaporated until formation of an organic matrix with uniform distribution of bismuth and alkali-earth metal atoms. Then a crystal lattice of photocatalyst is formed at 650-750 °C. When purifying water from organic contaminants using photocatalyst, weight ratio of purified water to weight of photocatalyst is selected from interval of 1000/1-1600/1, and irradiation with visible light of water with organic pollutants is carried out for 3-4 hours.

EFFECT: method enables to obtain particles of bismuthate of alkali-earth metal with an inhomogeneous composition, in form of a heterostructure of bismuth oxide, coated with bismuthate of alkali-earth metal of stoichiometric composition with degree of oxidation of calcium, equal to two, without defects in crystal lattice with low specific surface area without pores, as well as reduced consumption of photocatalyst during water treatment due to reduction of average particle size of photocatalyst and broader functional capabilities.

4 cl, 2 tbl, 59 ex

FIELD: chemistry.

SUBSTANCE: method of producing a photocatalyst based on alkaline earth metal bismuthate is to dissolve a mixture of bismuth nitrate Bi(NO3)3 and inorganic salt of alkaline earth metal Me, followed by standing of the products of their hydrolysis to form particles with bismuth ions evenly distributed by their volume and unevenly distributed alkaline earth ions and removal of excess moisture from the hydrolysis products, heating the produced particles to form particles as a heterostructure from amorphous by structure and stoichiometric by composition alkaline earth metal bismuthate and amorphous by structure and stoichiometric by composition bismuth oxide Bi2O3 followed by their crystallization. Herewith as inorganic salt of alkaline earth metal Me, alkaline earth metal oxalate MeC2O4 is taken, before dissolving alkaline earth metal oxalate MeC2O4 is purified from the adsorbed compounds and mixed with bismuth nitrate Bi(NO3)3, maturation of the products of their hydrolysis leads to the formation of particles of alkaline earth metal oxalate MeC2O4 impregnated with ions Bi(OH)2+, with evenly distributed bismuth ions and unevenly distributed alkaline earth metal ions, removal of excess moisture from the products of hydrolysis leads to the formation of precursor-particles in the form of heterostructures with the central part of alkaline earth metal oxalate MeC2O4impregnated with ions Bi(OH)2+ and the outer shell of bismuth hydroxonitrate Bi(OH)(NO3)2, heating the precursor-particles is carried out at two stages to form alkaline earth metal carbonate MeCO3impregnated with ions Bi(OH)2+, in the central part of each particle in the first stage and up to the formation of amorphous particles in the form of heterostructures with a central area of amorphous by structure and stechiometric by composition alkaline earth metal bismutite and the surface layer of the amorphous by structure and stechiometric by composition bismuth oxide Bi2O3 at the second stage, crystallization leads to the formation of particles of the photocatalyst in the form of heterostructures with the central area of crystalline by structure and stechiometric by composition alkaline earth metal bismutite and the surface layer of crystalline by structure and stechiometric by composition bismuth oxide Bi2O3. For mixing, the components are taken in the following ratio, wt %: alkaline earth metal oxalate MeC2O4 4.49-3.63, bismuth nitrate Bi(NO3)3 95.51-96.37, dissolution is carried out in distilled water with the following ratio of components, wt %: mixture of alkaline earth metal oxalate powders MeC2O4 and bismuth nitrate Bi(NO3)3 5.00-15.00, distilled water 95.00-85.00, heating of precursor-particles at the first stage is carried out up to 520°C with a heating rate of 0.5-1.0°C/min, at the second stage - up to 810°C with a heating rate of 1.0-2.0°C/min, the crystallization is carried out at a temperature of 750-825°C.

EFFECT: increasing the lifetime of the catalytic properties of the photocatalyst.

1 tbl, 20 ex

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