SU936803A3 - Process for producing aromatic c6-c10 hydrocarbons - Google Patents

Abstract

A method for producing shaped articles from fibrous and mineral industrial waste materials, comprising depositing a layer of an aqueous slurry composed of a mixture of a fibrous component and a mineral component; controlling the water content of the slurry to produce a coherent, agglomerated layer having a degree of wet strength; then shaping the layer under pressure; and removing it to produce a shaped article.

Description

(5) METHOD FOR PRODUCING AROMATIC HYDROCARBONS

1

The invention relates to methods for producing aromatic hydrocarbons Cg-C.pM can be used in the oil refining, petrochemical, shale chemical and coke chemical industries.

.. ....

A method for obtaining aromatic hydrocarbons by the interaction of toluene with synthesis gas is known.

The process is carried out, for example, at a pressure of 52.5 atm in the presence of a crystalline oxide catalyst containing CrO-, ZnO in a mixture with zeolite.

The disadvantage of this method is the low yield of aromatic hydrocarbons Cg, not exceeding E,E. A method for obtaining p-xylene by converting isobutylene in the presence of an oxide catalyst containing MgO 2. i is known.

The disadvantage of the method is the low yield of p-xylene, not exceeding 71.

io

Closer to the proposed method is the production of aromatic hydrocarbons by converting synthesis gas at 300-350°C, pressure

5 36-52.5 atm in the presence of a crystalline oxide catalyst containing a mixture of copper, iron, chromium and Y-type zeolite oxides. This produces 8.9 catalysate containing

10% aromatic hydrocarbons 40.7; alkenes 39, paraffin hydrocarbons 20.3 GC.

However, in this method of obtaining aromatic hydrocarbons, the yield of aromatic hydrocarbons per feedstock is not high, and does not exceed 5%. The purpose of the invention is to increase the yield of the target product.

20. The stated objective is achieved in that, according to the method for obtaining aromatic hydrocarbons from a raw material selected from a group containing isobutylene or methanol, or W-hexadecane, or a gas mixture of hydrogen and carbon monoxide, or methanol and methanol, by carrying out the process at a pressure of 30 atm using as a catalyst crystalline silicate, thermally stable at 600-1050 0, absorbing 6-8.2 weight of water at 25 °C and the pressure of saturated water vapor and after drying in a vacuum at having a powder X-ray diffraction pattern containing the reflections given in Table 1, containing the following components, weight: 0.1-0.2 Sodium oxide 5.5-8.0 Iron oxide 1.7-2.2 Aluminum oxide 0.7-0.8 Silicon oxide The rest Sodium oxide 0.05-0.2 0.8-8.0 Iron oxide 0.15-0.7 Water The rest Silicon oxide Crystalline silicate contains chromium oxide and zinc oxide. The results of the powder diffraction pattern are shown in Table 3 Continuation of Table 1 Radiation, Note wavelength 0, HM.VS very strong; S strong, M - medium; W - weak, - angle value according to Bragg's law, Example. Obtaining silicates 1-12. Silicate 1. A mixture of Fe(NO2), SiO, NaNO3 and (N2CH3) in water having a molar composition of Na2O4.5 Fe2O3 SiO2; is heated with stirring for 48 h in an autoclave at autogenous pressure. After cooling the reaction mixture, the resulting silicate is filtered, washed with water until the pH of the washing water is approximately 8, and dried for 2 h at . The thus obtained silicate 1 has the following chemical composition: 0.67 L(C,H2O)23O23Na2O23SO4SiO2O2-9N2O Silicate 2. This silicate is obtained like silicate 1, but the starting material is an aqueous mixture having a molar composition of: - «,5 G(C,H7)4 N2O2 i(Q, 5 Fe2.0 29.1 468 lij). The silicate 2 obtained in this way has the following chemical composition: 0.80 C(C5H,LN.p .0.30 Na.O- Fe.O, x X 45 Si02..13 HjO: Silicate 3. This silicate is obtained like silicate 1, but the starting material is an aqueous mixture that, in addition to FerNOj) contains ALCNOj) and has the following molar composition: . ,5 -(-0.33 ,- 0.67. . 29.1 N3.0. The silicate 3 obtained in this way has the following chemical composition: 0.55 (CjHyLNjiO- 0.45 Naap x X 0.67 , - 0.33 Al,jO . 30 SiO x X 10 HiO. Silicate k. This silicate is obtained like silicate 3, but the starting material is an aqueous mixture having the following molar composition: Na2O3 + 1.0 x 10.5 x 10.5 x 0.5 x 0.5 x 0.5 x 0.5 x 0.5 x 0.5 x 0.2 x 0.1 ... (CjH,) 0.2 Na O X X .-21.6 SiOa- . Silicate 6. This silicate is obtained as silicate I, but the starting material is an aqueous mixture that does not contain FeCN0,)3 and has the following molar composition: ,5CCCHN0,) x 29.1 SiO. 30 . . The resulting silicates 1-6 have a powder X-ray diffraction pattern as shown in Table 2. . T a b l e 2

Note. “The values of thermal stability of silicates 1-6 and the amount of water that they absorb after dehydration at 100 C in a vacuum at 25 C and at saturated water vapor pressure are given in Table 3. The composition of the obtained silicates in wt.% is given in Table .

Powder X-ray diffraction pattern of silicate (radiation: CXa-KL, wavelength 0, nm). g

Table 3

intensity of the strongest characteristic found in the radiograph, SP - sharp, SR - shoulder; NL - normal; BD - wide; Q - angle according to Bragg's law.

Silicates 7-12.

Using silicates 1-6 as the starting material, silicates 7-12 are obtained, respectively, by successive stages of calcining silicates -6 for k h at 500 C, boiling with a 1.0 M solution, washing with water, subsequent boiling with a 1.0 M solution of NbLNO and washing, drying for 2 h at and calcining for k h at . Composition of the obtained silicates, parts by weight:

Silicate 7 - 0.85 H, 0.05 Na O x X 30 SiOj.

Silicate 8 - 1,, 0,05 Na,j,0 x X Fe2.05 5 SiO.

Silicate 9 - 0.95 0.05 Na/jO x X 0.67 Fe O 0. Of the silicates 1-12 described in the invention, only silicates 1-, 7-to, are the proposed silicates. Silicates 5,6, 11 and 12, which do not contain iron, are not the subject of the invention and are included for comparison. In the proposed silicates, the negative electrovalences of iron and/or aluminum are compensated by replaceable cations in such a way that for each atom of iron and/or aluminum 55 there is one monovalent cation. Example 2. Obtaining p-crylol from isobutylene. Tests of silicates I and I2 are being conducted as catalysts in the production of rti-xylene from isobutylene. For this purpose, isobutylene is passed over a fixed bed of these silicates at atmospheric pressure and a space velocity of . The results of these experiments are given in Table 5.

The results presented in the table show the advantage of iron-containing silicates as catalysts for the selective production of p-xylene from isobutylene (experiments 1-3) compared to the corresponding silicates that do not contain iron (experiments and 5).

The compositions of the liquid products obtained in experiments 1–5 are given below.

Experiment 1. Composition of liquid product. weight:. .

Benzene0.3

Toluene3 8

p-Xylene6,4

o-Xylene3,3

. NV-XyleneZ,

Cft-Aromatic hydrocarbons 20.3 and above aromatic hydrocarbons Naphthenes + paraffins + f olefins 18.8

Experiment 2. Composition of liquid product, wt.%

Benzene0.2

/ Toluene3.0

P-Xylene11.3

o-Xylene0.6

M-Xylene0.6

Cft-aromatic hydrocarbons 16.3 and above aromatic hydrocarbons35.0 Naphthenes paraffins h + ole-Finm 331 P

Experiment 3. Composition of the liquid product,

es.%: . .

Benzene0.2

Toluene2.2

. ;p-Xylene6,8

O-Xylene2,4

M-Xylene 2.5, Cj-aromatic hydrocarbons 11.3 and higher aromatic hydrocarbons 30.7 Naphthenes + paraffins + olefins 3.3 Experiment A. Composition of the liquid product,

esd:

Benzene0.2

Toluene3

P-Xylene3.9 O-Xylene6.9 M-Xylene6.8 CQ-aromatic hydrocarbons17.8 and higher aromatic hydrocarbons38.3 Naphthenes + paraffins + olefins22.7 Experiment 5. Composition of liquid product, es. %:

Benzene0.1

Toluene0.5

p-Xylene0.4

O-Xylene0.6

M-Xylene0.5 Sd-aromatic

hydrocarbons2.9 and higher aromatic hydrocarbons6.2 Naphthenes + paraffins + olefins 88.2 Example 3 - Obtaining aromatic compounds from methanol. Silicate 8 was tested as a catalyst in obtaining aromatic compounds from methanol. For this purpose, the methanol was passed over a fixed bed of 5 atm. From this silicate at a pressure of 100 parts by weight of methanol as the starting material, 28.7 wt % of a mixture of liquid oxygen-free organic compounds was obtained. The average number of carbon atoms in this mixture was 9.5. The mixture contains 59.6% by weight of aromatic hydrocarbons distributed as follows in the form of various compounds, wt.%: Benzene Toluene P-Xylene M-Xylene O-Xylene Co-Aromatic hydrocarbons -Aromatic hydrocarbons Non-aromatic hydrocarbons are present in the liquid product in the following amounts, wt.%, based on the liquid product: Pentanes Cyclopentanes Hexanes Cyclohexanes Heptanes and higher-boiling paraffins Cycloheptanes and other higher-boiling naphthenes The gas has the following composition, wt. Propane Butanes p 4. Obtaining aromatic gasoline from n-hexadecane. Silicate 9 was tested as a catalyst in obtaining aromatic gasoline from n-hexadecane. For this purpose, hexadecane is passed over a fixed bed of this silicate at a pressure of 5 atm, 375°C and a volumetric growth rate of 1 h. The feed material is completely converted into a product having the following composition, wt.: 13-23.0 . , -Sur. The resulting liquid product has the following composition, wt.%: Benzene Toluene P-Xylene o-Xylene M-Xylene Cl-Aromatic hydrocarbons and higher aromatic hydrocarbons Olefins 10.0 Naphthenes 20.0 Paraffins 25.0 Example 5. Obtaining silicates 13-23. Silicates Silicate 13 is obtained like silicate 1, the only difference being that the aqueous mixture has the following molar composition: 0.8 (C3li,l4Nj-iO ..0.3 NaO-Fe-Q. x X 200 SiO-j.- 55 H2O. Silicate 1 is obtained from silicate 13 in the same way as silicates are obtained from silicates 1-6, respectively. Silicate 15 is obtained from silicate 13 by successive stages of calcining silicate 13 for k h at 500 °C, boiling with a 1.0 M solution, washing with water, subsequent boiling with a 1.0 M solution of NaNO and washing, drying for 2 h at and calcining for 4 h at 500 C. The silicate thus obtained 15 has the following chemical composition: X 200 SiO2. Silicates 16 and 17. Silicate 16 is obtained in the same way as silicate 1, but the starting mixture is an aqueous mixture that does not contain NaNO and has the following molar composition: 1.5 UCjHy) NjjPFe p.,, x x 205 310450-I2.0. Silicate 17 is obtained from silicate j6 by calcination for 4 hours at 500 C;. Silicates 18 and 19. The first mixture, containing 6.18 g of n-butylamine, 6.2 g of liquid glass (28 SiO2, 8 Na2O) and

56.2 g of water are mixed with a second mixture containing 1.3 g of Fe(804)5-9, 3.75 g of HjSQi and 77 g of water. The mixture thus obtained is stirred for 2 h at room temperature and then heated for 8 h with stirring in an autoclave at autogenous pressure. After cooling the reaction mixture, the resulting silicate is filtered off.

The powder X-ray diffraction pattern (C-K radiation, wavelength: 0. nm) of these silicates is given in Table 7.

Claims (3)

Table 7 Continuation of table. / Silicate 22. A mixture of Fe(NO)i, SiO2, NaCH and (in water, having a molar composition of 16:32 (510,-7200) is heated with stirring for 2 hours in an autoclave at 15°C under self-pressure. After cooling the reaction mixture, the resulting silicate is filtered, washed with water until the pH of the washing water reaches approximately B and dried for 2 hours at 120°C. Silicate 22 obtained in this way has the following chemical composition: 0.7(t( 0.23 - P3O3; SiO2-9 H... . . . Silicate 23. Silicate 22 is calcined for 4 hours at 500°C, then boiled with 1.0 N nitrate solution. ammonium and washed with water, then boiled again with 1.0 ammonium nitrate solution, washed, dried for 2 hours at 100 °C and calcined for 1 hour at 100 °C. Silicate 23 obtained in this way has the following chemical composition: 0.9 HJX 0.05 Fe2.0«v340 SiO. Of the silicates 13-23, only silicate 21, which is an amorphous product, is not covered by the scope of the present invention and is included for comparison. The compositions of the silicates in wt. are given in Tables k, . Example 6. Single-stage production of an aromatic hydrocarbon mixture from a mixture. The catalyst is prepared by mixing silicate I with a mixture consisting of 71.7 wt. ZnO and 28.6 wt. D in a weight ratio of 1:5. Both components are present in the catalyst in the form of particles with a diameter of 0.1-0.3 mm. The composition of the catalyst is as follows, wt.% 0.083 0.2167 SiO., 16.4167 H2O. 0.0250 ZnO 59.5000 23.8333 This catalyst was tested for the one-stage production of an aromatic hydrocarbon mixture from a mixture of .. The test was carried out in a 50 ml reactor, in which there was a fixed catalyst bed of 7.5 ml. The mixture, at a molar ratio of 2:1, was contacted with the catalyst at a pressure of 30 atm and a space velocity of ml gas/l catalyst/h. The results of this experiment were as follows: CO conversion, 75 H2 conversion, % 35 Composition of the products obtained, wt. Based on hydrocarbons ,8 Cj10.3 Cz15.9 C4t2.7 And higher Obtained liquid products have the following composition, eec.%i Benzene0.2 Toluene 1.8 p-Xylene 6.7 o-Xylene 3.3 m-Xylene 3.4 C-aromatic hydrocarbons 25.0 C-aromatic hydrocarbons15.2 C and higher aromatic hydrocarbons 7.9 Paraffin Ch-olefins 14.0 Naphthenes 22.5 Example 7. Obtaining aromatic gasoline from n-hexadecane aromatic gasoline from I-hexadecane. For this purpose, I-hexadecane is passed over a stationary layer of this silicate at a pressure of 5 atm, 375 °C and a space velocity of 1 . The feed material is completely converted into a product having the following composition, wt.% Benzene0.1 TolueneJ,lt P-Xylene3 6 o-Xylene1; 7 m-X-siol1.7 Cg-aromatic hydrocarbons12.5 and higher aromatic hydrocarbons16.7 Olefins10.0 Naphthenes23.0 Paraffins27.0 Example 8. Obtaining P-xylene by methylation of toluene. Silicate 14 was tested as a catalyst for obtaining p-xylene by methylation of toluene. For this purpose, a mixture of toluene and methanol in equivalent amounts was passed over a moving bed of this silicate at a pressure of 5 atm and a volume growth of 1 hour. The results of the experiment are as follows: Conversion of toluene, wt.% Conversion of methanol, wt.% Selectivity to Cg-aromatic hydrocarbons, % Amount of p-xylene in the Cg-aromatic fraction, % The total product obtained has the following composition, wt.: Methane0.1 Ethane + ethylene 0.5 Propane + propylene 1.4 Butanes + butylenes 2.0 Pentanes + pentenes 3.0 Benzene0.1 Toluene49.0 o-Xylene3.2 GL-Xylene3.3 P-Xylene26.5 C(, -aromatic hydrocarbons 2.9 -aromatic hydrocarbons 3.0 (and higher aromatic hydrocarbons 5.0 3 I Example 9. Obtaining aromatic compounds from methanol. Silicate 23 was tested as a catalyst for obtaining aromatic compounds from methanol. For this purpose, methanol is passed over a fixed bed of this silicate under a pressure of 5 atm, and a feed rate of 1 h . Using 100 parts by weight of methanol as a feedstock, 35 parts by weight of liquid, oxygen-free compounds are obtained. The average carbon number in the mixture 8.7. The mixture contains 32 wt.% Cg and higher aromatic compounds distributed over various compounds as follows, wt.; C 0.1; C 2.9 1-Cd3.1; M-Cg 2.4; 0-Cg 4.0; C 12.5 C,o 7.0. . Thus, the use of crystalline ferrosilicates in the processes of obtaining aromatic hydrocarbons 6 P° makes it possible to increase the yield of aromatic hydrocarbons. Claims of the invention i. A method for obtaining aromatic hydrocarbons by converting a feedstock at elevated temperature and pressure in the presence of a crystalline oxide catalyst, characterized in that, in order to increase the yield of the target product, compounds selected from the group containing isobutylene or methanol, or Ktexadecane, or a gas mixture of hydrogen and carbon monoxide, or a mixture of toluene and methanol, and the process is carried out at 350-400 ° C, a pressure of 130 atm using as a catalyst a crystalline silicate that is thermally stable at 600-1050 C, absorbing 6-8.2% (weight %) of water at and the pressure of saturated water vapor and, after dehydration in a vacuum at , having a powder X-ray diffraction pattern containing the reflections given in Table 1. containing the following components, by weight: 0.1-0.2 Sodium oxide 5.5-8.0 Iron oxide 1.7-2.2 Aluminum oxide 0.7-0.8 Water The rest is silicon or 0.15-0.0 sodium 21 936803.22 Iron oxide 0.8-8.0 ,02.08.77t as the initial syVoda O,15-0,/Or use a gas mixture of hydrogen Silicon oxide. The rest is carbon monoxide. 2. Method POP.1, difference-Sources of information, sh sh i i s   that the crystalline-s taken into account during the examination ki silicate contains chromium oxide and 1. US Patent (G C086289, zinc oxide. class 260-671H, published 1978. Priority on features: 2. Japanese Patent H SB-ltOSS, 16.12.76-B as the original source sy-cl. 16 C 1, published 1978. ry use isobutylene or meta-10 3. US Patent No. tl 39550, NOL, or N-hexadecane, or mixture of to-cl. 26Q-kk3, published 1979 (protog lurla and methanol. type).