THE CATALYST FOR OBTAINING OF FURAN

Химия и химические технологии/6. Органическая химия

c.ch.n. Bitemirova А. Е., c.ch.n. Baimenoba U.S., c.t.n. Assilbekova A.D.

International Kazakh-Turkish university named after H.A.Yassawi, Shymkent

The catalyst for obtaining of Furan

Resume: Increasing of catalyst activity for decarbonizing of Furfurol into Furan is reached in results of modifying of the 1% Pd/ Sibunit putted catalyst by addition of Co and Ni.

As a result of research the Furan output reaches up to 97-98 %, and the stability - 407-408 hours.

The oxided Zn-Cr-Mn catalyst for decarbonizing of Furfurol was earlier known [1]. However it poorly productive, it is quickly nonactivated, process is carried out at rather severe conditions, that causes the intensive Furfurol pitching. The “Pd at a corner” catalyst (КDF-1), consisting from 96,5 % of coal of the mark АРВ, 1,8 % Рd and 1,5 % Сs, had been studied in work [2]. However the specified catalyst has the low activity, and it is astable. Also the putted Pd/ Sibunit catalysts [3] is investigated for hydrogenization of Furfurol in Furfuril spirit.

The purpose of the present work is the study of the catalytic activity of the Pd catalysts, putted on the Sibunit (porous carbon received from carbohydrates raw material of petroleum), in reactions of Furfurol decarbonilization.

Preparation of catalysts. For obtaining of 40 g of the 1 % Pd on the Sibunit (Pd\ C *) the 0,34 g PdCl₂ and 0,68 g NaCl are dissolved in 100 sm³ of the distilled water at 40-50 ⁰C at continuous mixing till complete dissolution of PdCl₂ within 0,5 hours. The 40 g of Sibunit powder is added in a solution and mixed within 1 hours. Then the dropped out deposit is filtered and washed by water from Cl^-ions and dried up in a drying case at 110-150 ⁰С.

Further the depositing of Co or Ni on the granules (size - 1-2 mm) of the 1 % Pd\ Sibunit catalysts are carried out by a method of sedimentation from a water solution of the Co(NO₃)₂ or Ni( NO₃)_2. After complete sedimentation of the specified metals ions (visually is checked by a change of colour of a solution and by chemical methods of the analysis) on the carrier the catalysts are washed out, are dried in a drying case at 110 ⁰С within 24 hours.

Activity of the Pd\ Sibunit catalysts with the Co and Ni additives is tested on the flowing device for reaction of continuous experience. Take the 40 g of the catalyst with diameter of granules 1-2 mm and Furfurol that freshly overtaked, previously purified above CaO.

Activation of catalysts are carried out in reactor at 180⁰С for 1 hours and at 220⁰С for 2 hours in a current of hydrogen. The products of reaction are analyzed on the chromatograf "LHМ - 8МD". The activity of the catalyst is expressed in percentage of Furfurol conversion from transformed Furfurol; the stability of the catalyst – from the time of realization of the Furfurol decarboniliuzation.

Results of continious Furfurol decarbonilization on the modified additives of the Co Pd/Sibunit catalysts are presented in the table 1.

Table 1 - Furfurol decarbonilization on the Pd\ Sibunit catalysts modified by the Co additives. Temperature 160-280 ⁰С, 280-380 ⁰С

Compound of catalyst, mass.%

Time of experien

ce,

hour

The average output of decarbonilization products, %.

Activity,%

Selectivity,%

Pd: Co: Sibunit

Ф-н

С-н

ТГФ

Ф-л

0,8 0,5 98,7

Total

1,0 0,8 98,2

Total

1,0 1,2 97,8

Total

1,2 2,0 96,8

Total

For comparison

0,7 0,4 98,9

Total

1,3 2,1 96,6

Total

1,0 - 99,6

Total

Known coal of the mark 1,8 1,5 АРВ 96,6

Total

225

150

375

238

156

394

247

160

407

243

156

399

210

160

370

234

147

381

213

141

354

161

109

307

96,5

96,0

97,0

96,2

97,2

97,0

98,0

96,7

95,5

93,2

95,0

94,5

97,0

92,5

93,3

93,2

82,5

1,2

1,5

0,9

0,7

0,5

0,4

0,2

0,7

1,4

1,8

0,1

0,6

1,3

1,5

1,76

1,70

1,3

1,5

1,8

2,0

1,8

2,3

1,5

2,0

1,3

0,4

1,2

2,0

0,7

2,0

0,7

0,5

0,6

0,5

0,7

1,0

0,3

0,2

0,3

0,5

1,5

4,0

3,3

2,5

0,8

3,5

4,0

1,0

14,0

99,0

99,3

99,7

98,9

99,5

99,7

99,4

98,6

96,5

98,0

97,5

99,2

96,5

96,0

96,5

85,5

97,5

96,6

97,3

98,0

97,3

98,3

97,3

96,8

96,6

96,2

95,0

97,8

95,8

97,2

96,5

From table is visible, that the catalysts with the Co additives both on activity, and on stability surpass the catalysts without Co and industrial KDF-1. The greatest activity approximately 99 % and stability 394-407 hours the 1 % Pd\ Sibunit catalysts modified by 0,8-1,2 % Co are revealed, the output of Furan reaches 97-98 %.

Tests for 0,8-1,2 % Pd\ Sibunit catalysts modified by Ni additives within the limits of 0,5-2,0 % to weight of Sibunit similarly are carried out.

The results of Furfurol decarbonilization are given in the table 2.

Table 2 - The results of Furfurol decarbonilization on the Pd/Sibunit catalysts, modified by Ni additives

N	Compound of catalyst, mass.%	Time of experien ce, hour	The average output of decarbonilization products, %.				Activity,%	Selectivity,%
N	Pd: Ni: Sibunit	Time of experien ce, hour	Ф-н	С-н	ТГФ	Ф-л	Activity,%	Selectivity,%
1	2	3	4	5	6	7	8	9
1	2	3	4	5	6	7	8	9
1 2 3 4 5 6 7 8	0,8 0,5 98,7 Total 1,0 0,8 98,2 Total 1,0 1,2 97,8 Total 1,2 2,0 96,8 Total For comparison 0,7 0,4 98,9 Total 1,3 2,1 96,6 Total 1,0 - 99,6 Total Known coal of the mark 1,8 1,5 АРВ 96,6 Total	230 154 384 242 161 403 250 164 414 248 160 408 210 160 370 234 147 381 213 141 354 161 109 37 307	96,0 94,0 96.5 95.5 97,0 96,0 97.6 96,6 95,5 93,2 95,0 94,5 97,0 92,5 93,3 93,2 82,5	1,5 1,7 0,5 0,9 1.0 0,7 0,9 1.0 1,4 1,8 0,1 0,6 1,3 1,5 1,76 1,70 1,3	2.3 3.0 2.0 2.9 1,5 2,0 1,5 1.5 1,3 0.4 1,2 2,0 0,7 2,0 0,7 0,5 0,6	0,02 1.2 0.6 1,4 0,2 1.0 0,5 0,9 1.5 4.0 3,3 2,5 0,8 3,5 4,0 1,0 14,0	99,8 98.7 99,0 99.4 99,5 99,0 99,9 99,6 98,6 96.5 98,0 97,5 99,2 96,5 96,0 96,5 85,5	96.2 95.2 97,5 96.0 97.5 97,0 97.1 97,0 96.8 96,6 96,2 95,0 97,8 95,8 97,2 96,5 96,5

From the data of the table 2 follows that the Ni additive exert positive influence both on activity and on selectivity of the specified catalysts on the Furan. The stability is higher on 30-50 hours than at nonpromoted 1 % Pd\ Sibunit catalysts.

Literature

1. Karmilchik A.Ya., Giller S.A. Scientific basis of the catalysts selection and manufacture. Novossibirsk, 1964, P.225

2. Author certificate. USSR. №2613917 Kl. с 07 D 307/36

3. Beysekov T.B., Zhurhabayeva L.A., Bitemirova A.E. Hydrogenization of Furfurol on the putted Pd catalysts under the pressure of hydrogen. Magazine of applied chemistry. Т. 67. Release. 6. 1994 y.