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AZERBAIJAN CHEMICAL JOURNAL № 1 2022 ISSN 2522-1841 (Online)
ISSN 0005-2531 (Print)
UDC 542.943, 547.313.3, 549.67
A STUDY OF REACTION OXIDATIVE CONVERSION OF PROPYLENE TO ACROLEIN OVER CLINOPTILOLITE MODIFIED WITH 1.0 WT % Ni2+
T.I.Huseynova
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
Received 14.10.2021 Accepted 16.11.2021
The catalytic activity of natural and synthetic zeolites modified by ion exchange with cations Ni2+, Zn2+, Cu2+, Co2+, Bi2+ and Pd2+ in the reaction of propylene oxidative conversion by molecular oxygen to acrolein was studied. Based on the experimental data, it was found that natural clinoptilolite modified with Ni2+ cation exhibits the highest activity and selectivity in the reaction in question. The reaction conditions were studied.
Keywords: propylene, acrolein, zeolites, clinoptilolite, oxidation.
doi.org/10.32737/0005-2531-2022-1-64-67
Introduction
Acrolein is a feedstock in the production of acrylic acid, glycerol, methionine 1.3-pro-panediol, pyridine, glutaraldehyde, P-picoline, acrylonitrile, pharmaceuticals, herbicides, flavoring agents and plasticizers. From this point of view, obtaining the valuable product acrolein from the oxidative transformation of propylene has important theoretical and practical significance. Acrolein was first produced in the industry by catalytic condensation of acetaldehyde with formaldehyde. This method consists in passing a 30% aqueous solution of formaldehyde and acetaldehyde over silica gel impregnated with Na2SiO3 at 300-3200C. [1] The main disadvantages of the process are the formation of a large number of byproducts and the short life of the catalyst.
At present in industry acrolein is produced by heterogeneous catalytic oxidation of propylene. The most active and selective catalyst for vapor-phase oxidation of propylene to acrolein is copper oxide on carriers (0.1-1.5% Cu2O on pumice, carborundum, or Al2O3). Among the many complex oxide catalysts for the oxidation of propylene, molybdenum-containing catalysts are the most common. On molybdates, the reaction proceeds at a temperature of 400-500°C and a pressure of 0.1 to 1.0 MPa. On molybdates, the reaction proceeds at a temperature of 400-5000C and a pressure of 0.1
to 1.0 MPa. These catalysts achieve fairly high selectivity at short contact times and moderate temperatures. As a result of the reaction, the propionic aldehyde is formed along with acrolein. Purification of acrolein from near-boiling propionic aldehyde increases the cost of acrole-in. The disadvantage of the process is that the reaction proceeds at a high temperature and the yield of acrolein is very low [2-4].
Reactions of oxidative conversion of pro-pylene to acrolein are carried out mainly with the participation of catalysts modified with various metals containing Bi-Mo oxide. However, the oxidative conversion of propylene to acrole-in on metal-zeolite catalysts belongs to the poorly studied heterogeneous-catalytic reactions involving oxygen.
Experimental part
This paper describes the results of studies of the oxidative transformation of propylene into acrolein on modified synthetic (NaY, NaX, NaA) and natural (clinoptilolite and mordenite) zeolites of different crystalline structures. The zeolites used in this work were modified with several metal cations (Ni, Zn, Cu, Co, Cr, Mn, Fe, Mg, Mn, Bi, Pd, etc.), which were introduced into the zeolites by ion exchange in series. Natural zeolites were de-alloyed by acid treatment before the introduction of metal cations into them.
In the experiment, experiments were performed on a flow-through apparatus directly connected to an Agilent 7820 gas-liquid chromatography column. A 3 m long column filled with "PC" sorbent was used. Separation of the reaction products was performed under the conditions of a linearly programmed temperature rise of the chromatograph thermostat at a rate of 1.5 ml/min for the carrier gas (He). In the reactor made of pyrex glass with inner diameter dv=20 mm, with initial reaction mixture preheating and quenching zones, 4 cm3 of the catalyst with particle size 0.25-0.63 mm was loaded, activated in a current of hydrogen at 4500C for two hours, then the temperature was reduced to reaction temperature and the reaction mixture was fed with a certain volume rate.
Catalysts with a particle size of 0.250.63 mm and 99.2% propylene; 99.3% oxygen were used for catalytic activity studies. The obtained catalysts were activated by blowing with air at temperatures of 300-350°C and tested on a flow laboratory unit, the reaction unit of which was directly connected with a chromatograph. Separation of the reaction products was performed under conditions of linearly programmed thermostat temperature rise on an Agilent 7820 GC using a capillary column, HP-5-MS (30 m length).
The catalysts were synthesized by ion
exchange method. Synthetic zeolites such as NaY (SiO2/Al2O3=^=4.2), NaX (X=2.9), NaA (X=2.0) and natural zeolites such as mordenite (X=9.6) and clinoptilolite (X=10) of the Azerbaijan deposit modified by various metal cations (Ni2+, Zn2+, Cu2+, Co2+, Cr3+, Mg2+, Mn2+, Bi2+, Pd,Fe,
etc.). g.). Natural zeolites were treated with 0.5 N HCl solution before ion exchange. The amount of introduced cations in zeolite composition was determined by ion-spectral analysis on "ICP-MS Agilent 7700" device.
Translated with www.DeepL.com/ Translator (free version) Under the studied conditions (in the temperature range
320-3800C, volume rate 700-1500h-1 with the participation of molecular oxygen and molar ratio C3H6:O2=1.8:1) the transformation of propylene on synthesized zeolite catalysts occurred with the formation of acrolein, formaldehyde, formic acid [5].
As it was stated earlier from the data in Table 1 it follows that introduction of various transition and non-transition metal cations (Ni, Zn, Cu, Co, Cr, Mn, Fe, Mg, Mn, Bi, Pd, etc.) into clinoptilolite composition leads to changes in the activity of this catalyst. Thus, it was found that the influence of these metal cations is not the same, since each of these cations manifests itself differently in the reaction [6].
Experience number Cation content, % wt.. X, % S, % Reaction product yield, %
CO2 CH2O C3H4O HCOOH
1 Zn (0.2%) 37.5 5.25 22.13 13.4 1.97 -
2 Cu (0.5%) 58.25 - 38.65 19.6 - -
3 Co (0.5%) 59.81 - 46.37 13.44 - -
4 Mg (1%) 62.99 68.52 8.86 10.31 43.16 0.66
5 Pd (1%) 60.37 - 53.37 7.0 - -
6 Ni (1%) 94.72 85.44 5.44 5.75 80.93 2.6
7 Ni (3%) 69.83 68.85 11.96 4.19 48.08 5.6
8 Ni (5%) 74.0 48.7 25.74 8.02 36.04 4.2
9 CuFe (0.5: 0.25) 56.0 18.03 29.8 15.7 10.1 0.4
10 CuPd (0.5: 0.25) 50.03 - 50.03 - - -
11 CoBi (0.5: 1) 53.83 26.56 24.09 15.07 14.3 0.37
12 ZnCoCr (0.2:0.5:0.25) 68.35 65.0 14.96 8.4 44.43 0.56
13 CuPdZn (2:1:2) 65.52 - 65.52 - - -
14 CuMnCo (1:0.5:0.5) 51.41 16.69 33.25 9.34 8.58 0.24
Table 1. Oxidative conversion of propylene to acrolein on modified natural clinoptilolite (T=3800C, V0=700 h-1, CsH6:O2= 1.8:1)
66 T.I.HUSEYNOVA
Table 2. Results of experiments on the oxidative conversion of propylene to acrolein on 1% Ni2+clinoptilolite
Catalyst Temperature, 0C Volume velocity V0, h-1 Contact time, t, sec. Propylene conversion,% Acrolein yield, % Propylene selectivity, %
360 700 5.1 67.2 59.7 88.9
360 1125 3.2 63.6 57.4 90.2
360 1500 2.4 58.6 54.6 93.1
370 700 5.1 74.0 64.2 86.7
370 1125 3.2 69.6 61.8 88.7
1% NiH- 370 1500 2.4 65.1 58.7 90.1
clinoptilolite 380 700 5.1 84.5 75.6 89.4
380 1125 3.2 82.7 74.5 90.1
380 1500 2.4 76.2 70.3 92.3
400 700 5.1 90.3 72.9 80.8
400 1125 3.2 86.4 70.7 81.8
400 1500 2.4 81.5 69.0 84.7
The results of studies in the field of oxidative transformation of propylene on crystalline aluminosilicates showed that the reaction conditions, the zeolite structure, and the nature of the introduced cation have a significant influence on the direction of the reaction. The unique structural properties of natural zeolites, their high thermal and chemical stability, and their important role in the transformation of primary reagents and the formation of reaction products make it possible to synthesize highly effective catalytic systems for the catalytic oxidation of hydrocarbons.
This work aims to obtain acrolein with high selectivity and yield in the reactions of ox-idative transformation of propylene into acrole-in using a highly active metal-zeolite ca-talyst based on H-clinoptilolite zeolite (SiO2/ Al203=10) modified with cation 1% Ni2+.
The set task was achieved based on H-clinoptilolite zeolite modified with 1% Ni cation on the catalyst surface in the temperature range 3 60-4000C, molar ratio C3H6:02=1.8:1.
Table 2 shows the dependences of propylene conversion, acrolein yield and process selectivity at different temperatures. The highest acrolein selectivity of the process is 9293.1%
in the temperature range 360-3800C, the volume is observed at a rate of 1500 h-1, and conversion of propylene is 58.6-76.2%, acrolein yield 54.6-70.3%.
Thus, the set task was achieved based on H-clinoptilolite zeolite modified with 1% Ni2+ cation on the catalyst surface in the temperature range 3 60-4000C, molar ratio C3H6:02=1.8:1, volume rate 700-1500 h-1 and at contact time 2.4-3.2 sec.
References
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3. Lebedev N.N. Khimiya i tekhnologiya osnovnogo organicheskogo i neftekhimicheskogo sinteza. M.: Khimiya, 1998. 592 p.
4. Boreskov G.K. Geterogennyy kataliz. M.: Nauka, 1989. s. 197.
5. Aliyev A.M., Nadzhaf-Kuliyev U.M., Guseynova T.I., Sarydzhanov A.A., Safarov A.R., Bakh-manov M.F., Agayeva R.Yu., Yaryyev V.M. Neftepererabotka i neftekhimiya, TSNIITE-NEFTEKHIM. 2019. № 5. P. 25-30.
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1.0 % Ni2+ ÍLO MODÍFÍKASÍYA EDÍLMͧ KLÍNOPTÍLOLÍT ÜZORINDO PROPÍLENÍN AKROLEÍNO oksídlo§dír1cí cevrílmo REAKSÍYASININ TODQÍQÍ
T.Í.Hüseynova
Propilenin molekulyar oksigenla akroleim oksidlagdirici gevrilma reaksiyasinda Ni2+, Zn2+, Cu2+, Co2+, Bi2+ va Pd2+ kationlan ila ion mübadila üsulu ila modifikasiya olunmu§ tabii va sintetik seolitlarin katalitik aktivliyi óyranilib. Eksperimental naticalar asasinda müayyan olunmu§dur ki, tarkibinda 1.0 % Ni2+ saxlayan tabii klinoptilolit baxilan reaksiyada yüksak aktivlik va selektivlik góstarir. Reaksiyanin getma ¡jaraiti 6yranilmi§dir.
Agar sozlar: propilen, akrolein, seolitbr, klinoptilolit, oksidh§m3.
ИССЛЕДОВАНИЕ РЕАКЦИИ ОКИСЛИТЕЛЬНОЙ КОНВЕРСИИ ПРОПИЛЕНА В АКРОЛЕИН НА КЛИНОПТИЛОЛИТЕ, МОДИФИЦИРОВАННОМ 1,0 МАС.% Ni2+
Т.И.Гусейнова
Изучена каталитическая активность природных и синтетических цеолитов модифицированных методом ионного обмена катионами Ni2+, Zn2+, Cu2+, Co2+, Bi2+ и Pd2+ в реакции окислительного превращения пропилена молекулярным кислородом в акролеин. На основе экспериментальных данных установлено, что природный клиноптилолит, модифицированный катионом Ni2+ проявляет наиболее высокую активность и селективность в рассматриваемой реакции. Были изучены условия протекания реакции.
Ключевые слова: пропилен, акролеин, цеолиты, клиноптилолит, окисление.
