RU1322539C - Catalyst for hydrolysis of oxidized paraffin - Google Patents

Abstract

The invention relates to catalytic chemistry, in particular a catalyst (CT) for the hydrolysis of oxidized paraffin used in the manufacture of synthetic fatty acids. In order to increase the activity, QD-based and SiOjs additionally contain α-alkali metal oxide (OSHM), alkaline earth metal oxide (OSHM), FejOj and NaY zeolite in ion-decatonized form in an amount of 10-20 wt%. Composition of CT, wt.%: A1- | Oz 1.5-50.0; OSHM 0.1-1.0; OSHZM 0.2-2.0; FejO 0.03-0.8; SlOj the rest. The modified composition of the CT, wt.%: A1jQj1,5-50,0; OSHM 0.1-1.0; FejOj 0.03-0.8; OSHZM 0.2-2.0; rare earth oxide, 0.5-5.0; SiOj the rest. Another modified composition of the CT, wt.%: AljOj 50,0; OSHM 0.1-1.0; FcjOj 0.03-0.8; OSHZM 0.2-2.0; rare earth oxide 0.5-5.0; 0.1-1.0; SiOj the rest. The predominant jBse reduction and rare earth oxide increases the activity of CT. Testing of the indicated CT compositions during the hydrolysis of paraffin oxide shows that they provide better functional indicators of the hydrolyzate than in the known case in terms of acid, ether, carbonyl and iodine numbers, i.e. up to 60.5; 20.2; 8.1; 13.6 against 69.2; 32.1; 8.3; 17.5 with a degree of hydrolysis of 52.5 versus .42.5%. 2 s.p. f-ly. 1 tab.

Description

The invention relates to catalysts for the hydrolysis of oxidized paraffin in the production of synthetic fatty acids by oxidizing paraffin hydrocarbons with air oxygen,

The aim of the invention is to increase the activity of the catalyst due to the additional content in 1Nm of oxides of alkali and earth-earth metals, iron oxide (III) and zeolite SaY in an ion-decationized form with a certain content of components. In the prior art ™ catalyst, the additional catalyst containing zeolite NaY in a mixed cationic-reduced form with rare earth catalyst may additionally also contain oxhydryl,

The invention is illustrated by the following examples,

-Example 1. Preparation of ka - talizator no p, 1 formula

A solution of sodium silicate (207.4 kg / 1.5) and a solution of ammonium sulfate (410, 4 K1 / m) are mixed with a node suspension of MaY zeolite (100 kg / m in a ratio of 2: 1: 0.65 at 20 ° C in TC 2 hours After syneresis (12 hours), the resulting sol is coagulated into hydrogel balls in a layer of mineral oil.Then the balls of the datalizer are treated at -25 ° C three times for 15 hours in a ratio of 1: 2 with a solution (Ukg / m ammonium nitrate. After that the kata. piper is washed at 25 ° C; with steam condensate. Two times at a ratio of 1: 2, dried at 150 ° C for 5 hours and calcined at 5 hours in a stream of air. gidy (W%) in the catalyst ion-decationized form the following composition,

Aljoy

Fe, 0,

W. O 0.2 0.4

CaO —O, 5

SiOj88.9

Example 2. 500 g of paraffin oxide with the following national numbers;

Acid71.5

Essential55.8

Carbon 6.5. Iodine 1.2

Skip at 2.44

g

through a catalyst layer with an ohm of 50 ml.

n., sodium 5 is iron and calcium and represents balls with a diameter of 1–5 t with an average pore diameter of 60–80 L. 10 mass% of NaY zeolite in ion-decation form with an average diameter of 1 rum of pore are deposited on this matrix. 9--13 L. The catalyst as a whole has the composition, in May about% /

 :

G

5

A1.0, Na, O Fe, 0, CaO SiO.

1,., 0.1 0.03

.0,2

98.17

After hydrolysis, 492 g of oxidate are obtained with the following functionals - numbers: K to: lot Efg11): Karoon 5th Iodine

Deep hydrolysis And r to m in p 3 about 50Q g of oxidate and solid solid aarafip ;; 1 sec. The quality as in Example 2 is processed under the conditions of Example .., but 15% of HaY zeolite is applied on Iatrz and, on the catalytic converter, in decath-7oni.ro.wagy form, the Catalyst has the composition % $

A1.0,. 10.8 on Ol

63.8, 25 „8 6.0 15.7 54.0%

0.4

0.7

G, 7.D

0

O

After pshrolkaa receive 49A g of oxidate with the following functional chls:

64.5

22.6 6.4

i5.6

59.5%.

oxidate

Acid Essential Carbonyl Iodine

The depth of the hydroleague Example 4, 500 g of solid paraffin with the quality as in example 2j c is achieved under the conditions of example 2 on a catalyst, 20% NaY zeolite in iop-decahnated form is deposited on the TOROGO matrix C. The catalyst has a composition of .% Al OjSO, O

   1,0

 0.8 CaO. 2.0

SiOjL6.2

After hydrolysis, I get 1,490 g of oxidate with the following functional numbers of g

Acid62.8

Essential 24 SI

Carbonyl 7, I

Iodine14.6

Depth of hydrolysis 58.5% Example 5. 500 g of solid paraffin oxidate c. quality, as in example 2, is processed under the conditions of example 2 on a ball catalyst prepared; as in example 1, but for the synthesis of the matrix instead of sodium silicate, sodium silicate is used. The resulting catalyst has the following P51Y composition, wt.%:

10.2 O, 3

FejOj 0.3

CaO .0.8

A1.0, KjO

sic.

88.4

After hydrolysis on this catalyst, 492 g of oxidate are obtained with the following functional numbers:

Acid65.0

Essential 22.9

Carbonyl 6.5

Iodine15.0

The hydrolysis depth is 59.1%. Example 6. 300 g of solid paraffin oxidate with a quality as in Example 2 was treated under the conditions of Example 2 on a ball catalyst prepared as in the example, but a solution of magnesium chloride was used instead of calcium chloride solution n. The resulting catalyst has the following composition, wt.%:

A1,0,11,3

Najo 0.6

FejOj. Oh 5

MgO 3

SiOj87.3

After hydrolysis on this catalyst, 496 g of oxidate are obtained with the following functional numbers:

Acid64.0

. Essential 22.1

Carbonyl 6.5 Iodine 16.0

The hydrolysis depth is 60.4%. Example 7 (for comparison).

500 g of solid paraffin oxide from the quality, as in example 2, is treated at a feed rate of 2.44 with a 50 ml catalyst layer. The Thor catalysis matrix consists of a mixture of oxides of algomini, silicon, sodium, iron and calcium and consists of balls with a diameter of 1-5 mm. 5% zeolite NaY in

cationic form. The final catalyst has a composition, wt.%: AljO, 1.4

Najo 0.08

FOjO, 0.01

CaO0.1

SiOj98.41

After hydrolysis, 493 g of oxidate are obtained with the following functional numbers:

Acid64.5

Essential30.6

Carbonyl 6.5 Iodine 12.6

G of the depth of hydrolysis is 45.4%. Example 8 (for comparison). 500 g of solid paraffin oxidate with a quality as in Example 2 was processed on the catalyst under the conditions of Example 2. The matrix of the catalyst consists of a mixture of oxides of aluminum, silicon, iron and calcium and is a 1-5 mm bead. 25% of zeolite NaY in ion-decathionized form is applied to said matrix. The final composition of the catalyst has the following ratio of ingredients, wt.%:

, 3

NajO1.5

Ge ,, 0z1.0

CaO2.2

SiOj40,0

After digestion, 495 g of oxidate are obtained with the following functional numbers:

Acid66.5

Essential31.1

Carbonyl 7.2 Iodine 10.5

The depth of hydrolysis is 44.2%. Example 9. Preparation of the catalyst according to claim 2 of the formula.

A solution of sodium silicate (207.4 kg / m) and a solution of ammonium sulfate (410.4 kg / m) are mixed with an aqueous suspension of zeolite NaY (150 kg / m in a ratio of 2: 1: 0.65 at 20 s within 2 hours after syneresis (10 hours), the sol is coagulated into hydrogel beads into a layer of mineral oil, then the catalyst eggs are treated three times in a 1: 2 ratio for 5 hours with a solution (10 kg / m) of ammonium nitrate and then for 25 h with a solution of rare-earth elements (REE) (1.5 kg / m) in the form of Nitrates in a ratio of 1: 3 at 50 C, After that, the balls of processing 5 1322539

they are washed with a solution of ammonium nitrate (20 kg / m) at a ratio of 1: 2 once and washed with steam condensate of one pa at a ratio of 1s3. Then the balls are dried at 5 (3 h) and calcined in a stream of air for 8 hours at 550 C.

In this way, a catalyst is obtained containing 15% zeolite in cationic-decationized form with REE III of the following composition, wt.%:

12.0 0.2

, 2

CaO0.3 5

(P33) j033.0

ACO,

SiO

 I

84.3

A mixture of cerium laptan, 1 neodymium and 20 praseodymium is used as the rare-earth elements of the la cerium group.

Example 10, 500 g of solid paraffin oxddate with a quality as in Example 2 was treated at 250 ° C and an oxidate feed rate of 2, D 4 h-25 on a 50 ml catalyst. The matrix of the cauliflower consists of a mixture of oxides of aluminum, silicon, sodium, wood and calcium and provides balls with a diameter of 1

ok n

k t t n k

5 mm with medium

about a pore diameter of 60-80 A. On the specified

the matrix is applied with 10 wt.% zeolite NaY in mixed cation-decationized form with REE in the following ratio of ingredients in the final catalyst composition, wt.%:

1.5

ACO,

Fe, 0i CaO

(P33) iOj Sic,

0.1

0.03 0., 2 0.5 97.67

1

After hydrolysis, 495 g ok

Sidata with the following functional numbers: 30 °

35

40 about to to for 45 sha well wa m 50 and that

Acid64.3

Essential 22.1

Carbonyl 5, .8 Iodine 16.0

Depth: hydrolysis 60.5%. Example 11. 500 g of an oxidate with a quality as in Example 2 was processed under the conditions of Example 10 on a catalyst on the matrix of which 16% NaY zeolite in mixed cationic cationized form with REE was applied in the following ratio of ingredients, May.%;

A1.0

CaO

(P33) jOj SiO,

After hydrolysis, an oxidate is obtained with the following numbers; Acid Essential Carbonyl Iodine,

Depth of hydrolysis Example 12. 500 quality, as in the example, was tested under the conditions of an exemplary analyzer, 20% of the HaY zeolite and cation decathed with a goat earth element containing an iptredium ratio were loaded onto the matrix

Fe-jOj

CaO

(REE) GOZ

SiO

A1.0z Na, 0

After hydrolysis, 493 g of oxidate are prepared with the following: functional numbers:

Acid64.2

Essential 22.3

Carbonyl 6.3

YodnoeN, 2

The hydrolysis depth of 60.2%, Example 13 (comp. Comparison), 500 g of solid paraffin oxidate with a quality as in example 2j is processed on a zeolite catalyzer ™ tor in the conditions of example 10, The catalyst matrix consists of a mixture of aluminum oxides of silicon J is sodium, iron, and calcium and is. Ariks 1-3 m in diameter. 5 wt.% NaY zeolite in mixed cation-decationized form with rare earth elements is applied to the indicated matrix in the following ratio of ingredients in the final composition of the MaCi catalyst.% s. .

5

Na 0

,

CaO

(REE) g05

SiO

1,2

0.05 0.02 OJ5 0.20 98.38

Al, Gj

Fe.Oj

7

After hydrolysis, 495 g of oxidate are obtained with the following functional numbers:

Acidic 65.5 Essential29.7

Carbonyl 6.1 Iodine, 5

The hydrolysis depth is 46.9%. Example 14 (for comparison). 500 g of hard paraffin oxide, with a quality as in Example 2, are processed under the conditions of Example 11. The catalyst matrix consists of a mixture of alumina, silicon, sodium iron and calcium in the form of balls. 25 wt.% NaY zeolite in mixed cation-decationized form with REE is applied to this matrix with the following ratio of ingredients in the final composition of the catalyst, wt.%

53 2.0 1.0

CaO2, 5

(P33) j035.5

SiOj36.0

After hydrolysis, 492 g of oxvdate are obtained with the following functional numbers:

Acid64.8

-. Essential30.2

Carbonyl 6.5 Iodine 12.2

The depth of hydrolysis is 45.8%. Example 15. The preparation of the catalyst according to claim 3 of the formula,

A sodium silicate solution (207.4 kg / m) and a solution of ammonium sulfate (410.4 kg / m) are mixed with an aqueous suspension of NaY zeolite (200 kg / m in a ratio of 2: 1: 0.65 at 20 ° C for 5 hours After syneresis (12 hours), the hydrosol is coagulated into hydrogel beads into a layer of mineral oil.Then the catalyst balls are treated twice in a ratio of 1; 3 N for 4 hours with a solution (10 kg / m) of ammonium nitrate, then for 20 hours with a solution of rare-earth elements ( 2 kg / m in the form of nitrates in a ratio of 1: 4 at. After that, the hydrogel beads are treated with a solution of ammonium nitrate (20 kg / m) at 1: 2 ratio once, and then O, i and pacTfjtipoM are treated with chromium nitrate for 15 hours at 20 ° C at a ratio of 1: 3 and ripoNfi.innioT once at 20 ° C at a ratio of 1: 2 with steam condensate. h

2539 9

at and calcined for 8 hours at. in a stream of air.

After calcination, a catalyst is obtained containing 20% of type U zeolite in a mixed cation-decationized form with REE and chromium of the following composition, wt.%:

11.5

. 0.3 0.3

CaO 0.5

Cg, 0-0.20

(REE), OZ3.7

A1.0z Na, 0 o FejOj

5

SiO

83.5

Fe, 0,

5 Example 16, 500 g of oxidate with

quality, as in example 2, is processed under the conditions of example 10 on the catalyst in the form of balls with a diameter of mm, mean average pore diameter is 0 70-140 L, the catalyst has the following composition, wt.%:

AljO, 1.5

0.1 O, .03

CaO0.2

.0.1

(REE) ;; Oz0.5

SiO, 97.57

After hydrolysis, 49t g of oxidate are obtained with the following functional numbers:

Acid61.2

Essential-21.6

Carbon 1-6.5

5 Iodine14, A

The depth of hydrolysis is 61.25S. Example 17 500 g of an oxidate with a quality as in Example 2 is treated under the conditions of Example 10 on a catalyst with a composition of wt.%:

lg Oz25.0

0.4 0.4

CaO0.8

5CrjiO .. -0.5

(P33) j05.2.5

SiOj60.4

NajO Fe.O,

50 After pshchrolysis receive 494 g ok-, sidata with the following functional numbers:

Acid. 64.8

Essential 19.3

35 Carbonyl 6.9

Iodine16.2

The hydrodysis depth is 65.5%. Example 18. 500 g of oxide t with a quality as in example 2 are processed under the conditions of an example with a composition composition, wt.%:

1322539 10 on kataAljO,

Najo

Fe, 0,

CaO

Cr, 0

(P33) jO,

SiO

50 t, 0 0.8 2.0

no

5.0 40.2

fifteen

13.6

52.5%.

.5

A1.0z

Najo

FejO,

thirty

After hydrolysis, 490 g of idat are obtained with the following functional islam

Acid 60.5

Essential 2.0.2

Carbonyl 8, Iodine

Hydrolysis Depth Example 19 (for comparison). 500 g of solid paraffin oxidate a with a quality as in example 2, o0-20 are abutted on the catalyst under the conditions of example 10. The catalyst consists of 5% zeolite NaY in mixed ion-deionized form and from oxides of the following metals J in the ratio ae D

1.3 0.08 0.02

SaOO, 10

  0.05

(P33) jOj - 0.30 SiOj 9B „15 After hydrolysis, 494 g of xidate are obtained with the following functional numbers;

Acid63.8

Essential28.5

Carbonyl 6.9 Iodine 12.1

The hydrolysis depth is 47.3%. . Example 20 (comparison).

500 g of hard paraffin oxide, with a quality as in Example 2, are treated under the conditions of Example 10 with a catalyst containing 75% of an aluminum oxide matrix, sodium, iron, calcium, chromium and silicon and 25% NaY zeolite in a mixed cation - decationized form with REE with the following ratio of ingredients in the final state, wt.%:

35

40

45

fifty

si chi

fi pr and li with 89 di

ok hb

by

l t o l t

52 1.1 0.9 2.1

M

10

539

5

0

0

5

0

5

0

64.1 30.3 7.5 14.6 45.4%.

measures 21 (according to the prototype), solid vapor oxidate-I,

5

(P33) jOj5,2

Sic, 37.6

After hydrolysis, 495 g of oxidate are obtained with the following functional numbers:

Acidic

Ethereal

Carbonyl

Iodine

Hydrolysis Depth At 500 g

finas with quality, as in example 2, are passed at a feed rate of 2.44 h and a temperature of 250 s through a 50 ml catalyst bed. The catalyst consists of 10.8% alumina and 89.2% silicon oxide in the form of balls with a diameter of 1-3 mm

Obtain 490 g of hydrolyzed oxindate with the following functional HbnviH numbers:

Acidic

Ethereal

Carbonyl.

Iodine

Hydrolysis depth

69.2

32.1

8.3

17.5

42.5%

For comparison, the data obtained is tabulated.

Claims (1)

The claims t. A catalyst for the hydrolysis of oxidized paraffin in the production of synthetic fatty; acids, including-, alumina, and silica-alumina, with a temperature of 10 p and so that, with an increase in the activity of the catalyst, it additionally contains alkali metal oxide, alkaline earth metal oxide, selez (III) oxide and zeolite NaY in ion-decationized form in the amount of wt.% With the following contents of the components in terms of oxides, wt.%: Alumina oxide 1.5-50.0 Alkali metal oxide O, 1-1.0 Iron oxide (III) 0,) 3-0.8. Alkaline earth oxide metal 0.2-2.0 Oks1shch silicon The rest. 2, The catalyst according to claim 1, characterized in that, in order to increase the activity of the catalyst, it additionally contains JNaY zeolite in a mixed cation-decationion-11111322539 with rare earths, wt%, when the content of components in oxides, wt% 5 aluminum, 0 by he ma ko 5 ma 2539 2 In addition to the activity of the catalyst, it additionally contains chromium (III) oxide in the following content of components in terms of oxides, 5 maso%: