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ÓÄÊ 541. 128. 66. 094.   

                                  The catalyst for obtaining of Furan

Bitemirova  À. Å., Baimenoba U.S., Kerimbekova Z.M.

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

Shymkent, Kazakhstan

            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 (ÊDF-1), consisting from 96,5 % of coal of the mark ÀÐÂ, 1,8 % Ðd and 1,5 % Ñs, 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 0Ñ.

            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 0Ñ 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 1800Ñ for 1 hours and at 2200Ñ for 2 hours in a current of hydrogen. The products of reaction are analyzed on the chromatograf "LHÌ - 8ÌD". 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 0Ñ, 280-380 0Ñ

 

N

Compound of catalyst, mass.%

Time of experience,

hour

The average output of decarbonilization products, %.

Activity,%

Selectivity,%

Pd: Co:  Sibunit

Ô-í

Ñ-í

ÒÃÔ

Ô-ë

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  ÀÐÂ 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

37

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

 

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

 

99,7

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

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

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 experience,

hour

The average output of decarbonilization products, %.

Activity,%

Selectivity,%

Pd:   Ni:   Sibunit

Ô-í

Ñ-í

ÒÃÔ

Ô-ë

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  ÀÐÂ 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. ¹2613917 Kl. ñ 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. Ò. 67. Release. 6. 1994 y.