Process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof

Abstract

This invention discloses the process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof, hydrogenation of aromatic polycarboxylic acids or derivatives thereof can be achieved in the present of the catalyst, which consist at least one metal of the eighth transition group of the Periodic Table as the active metal while group IIA and group IVA elements are included as the catalyst support.

Claims

1. A process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof by hydrogenation of aromatic polycarboxylic acids or derivatives thereof with a catalyst in hydrogen atmosphere, wherein the catalyst comprises (1) an active metal of group VIIIB transition elements of the periodic table and (2) a catalyst support made from a combination of group IIA and group IVA elements of the periodic table.

2. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the active metal of the group VIIIB transition elements of the periodic table is platinum (Pt), palladium (Pd), ruthenium (Ru), nickel (Ni), rhodium (Rh) or any combination of the above.

3. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the catalyst support of group IIA elements of the periodic table is magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) or any combination of the above.

4. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the catalyst support of group IVA elements of the periodic table is silicon (Si), germanium (Ge), Tin (Sn) or any combination of the above.

5. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the active metal of group VIIIB transition elements, the catalyst support of group IIA elements and the catalyst support of group IVA elements are in the ratio of (10-80):(1-30):(1-30).

6. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein when the active metal of group VIIIB transition element is Ni, the catalyst support of group IIA elements is Mg and the catalyst support of group IVA elements is Si, the active metal of group VIIIB transition elements, the catalyst support of group IIA and the catalyst support of group IVA are in the ratio of (20-70):(1-20):(1-20).

7. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein when the active metals of group VIIIB transition elements is Ni, the catalyst support of group IIA elements is Mg and the catalyst support of group IVA elements is Si, the active metal of group VIIIB transition elements, the catalyst support of group IIA and the catalyst support of group IVA are in the ratio of (45-65):(2-15):(2-15).

8. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein when the active metals of group VIIIB transition element is Ni, the catalyst support of group IIA elements is Mg and the catalyst support of group IVA elements is Si, the active metal of group VIIIB transition elements, the catalyst support of group IIA and the catalyst support of group IVA are in the ratio of (50-65):(3-10):(5-12).

9. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the to specific surface area of the catalyst is between 80-300 m.sup.2/g, the pore volume of the catalyst is between 0.2-0.9 cm.sup.3/g, and the average pore size diameter of the catalyst is between 2-50 nm.

10. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the specific surface area of the catalyst is between 100-250 m.sup.2/g, the pore volume of the catalyst is between 0.25-0.7 cm.sup.3/g, and the average pore size diameter of the catalyst is between 5-30 nm.

11. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the specific surface area of the catalyst is between 120-200 m.sup.2/g, the pore volume of the catalyst is between 0.3-0.5 cm.sup.3/g, and the average pore size diameter of the catalyst is between 10-25 nm.

12. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the aromatic polycarboxylic acids are aromatic compounds form with carboxylic acids, dicarboxylic acids, polycarboxylic acids, hydroxycarboxylic acids or any combination of above in structure, and benzene polycarboxylic acids comprise phthalic acids, isophthalic acids, terephthalic acids, trimellitic acids, trimesic acids, hemimellitic acids, pyromellitic acids, or any combination of the above.

13. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the derivatives of aromatic polycarboxylic acids comprise monoesters, diesters and polyesters of aromatic polycarboxylic acids or any combination of the above, wherein the esters comprise C.sub.1-C.sub.30 alkyl esters, C.sub.3-C.sub.30 cycloalkyl esters, C.sub.1-C.sub.30 alkoxyalkyl esters or any combination of the above.

14. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the derivatives of aromatic polycarboxylic acids are esters comprising C.sub.2-C.sub.20 alkyl esters, C.sub.3-C.sub.20 cycloalkyl esters, C.sub.2-C.sub.20 alkoxyalkyl esters or any combination of the above.

15. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the derivatives of aromatic polycarboxylic acids are esters comprising C.sub.3-C.sub.18 alkyl esters, C.sub.4-C.sub.18 cycloalkyl esters, C.sub.3-C.sub.18 alkoxyalkyl esters or any combination of the above.

16. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the derivatives of aromatic polycarboxylic acids comprise dimethyl phthalate (DMP), dimethyl terephthalate (DMT), dimethyl isophthalate, diethyl phthalate (DEP), dibutyl phthalate (DBP), diisooctyl phthalate (DOP), diisononyl phthalate (DINP), benzyl butyl phthalate (BBP), diisodecyl phthalate (DIDP), dioctyl terephthalate (DOTP) or any combination of the above.

17. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the hydrogenation is carried out at pressure between 1-100 bar.

18. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the hydrogenation is carried out at pressure between 1-50 bar.

19. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the hydrogenation is carried out at pressure between 1-30 bar.

20. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the hydrogenation is carried out at temperature between 50-200 C.

21. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the hydrogenation is carried out at temperature between 50-150 C.

22. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the hydrogenation is carried out at temperature between 50-100 C.

23. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the aromatic polycarboxylic acids or derivatives thereof can be mixed with solvent or diluent.

24. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein operating type of the process comprises batch type, semi-batch type, continuous type or any combination of the above.

25. The process for hydrogenation of aromatic polycarboxylic acids or derivatives thereof to the corresponding alicyclic polycarboxylic acids or derivatives thereof as claimed in claim 1, wherein the hydrogenation is carried out in a reactor comprising a batchwise, stir tank, trickle bed, bubble column, multi-tube or any combination of the above.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Preparation Example 1: Preparation of Catalyst A

(1) 53.5 g of nickel nitrate and 9.5 g of magnesium nitrate were dissolved and mixed in 300 mL of deionized water to form a solution. Next, deionized water containing ammonia water, sodium carbonate or sodium hydroxide (or a mixture of any two of above), were added into the solution for adjusting pH to 9-11 and stirred completely at 60-90 C. 6 mL of sodium silicate solution was subsequently added into the above solution and continuously stirred for 1-4 hours. The stirred solution was then filtered to give a filter cake. After washed and dried at 110 C., the filter cake was calcined at 700 C. for 4 hours to obtain a catalyst A.

Preparation Example 2: Preparation of Catalyst B

(2) 53.5 g of nickel nitrate and 19.1 g of magnesium nitrate were dissolved and mixed in 300 mL of deionized water to form a solution. Next, deionized water containing ammonia water, sodium carbonate or sodium hydroxide (or a mixture of any two of above), were added into the solution for adjusting pH to 9-11 and stirred completely at 60-90 C. 24 mL of sodium silicate solution was subsequently added into the above solution and continuously stirred for 1-4 hours. The stirred solution was then filtered to give a filter cake. After washed and dried at 110 C., the filter cake was calcined at 700 C. for 4 hours to obtain a catalyst B.

(3) The present invention provides a hydrogenation reaction of aromatic polycarboxylic acids and derivatives thereof using the catalyst containing a catalyst support and active metals. The hydrogenation reaction is carried out using di(2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP) and diisononyl phthalate (DINP) as reactants. The reaction conditions and results are described as follows.

Embodiment 1

(4) 7 mL of the catalyst A (20-30 mesh size) was filled in a reaction tube and reduced at 450 C. in hydrogen atmosphere. After cooling, the reactor was fed with di(2-ethylhexyl) phthalate (DOP, DEHP) by pump to perform hydrogenation reaction. After the reaction, the products were collected for quantitative measurement. The conversion and selectivity were analyzed by liquid chromatography-UV (LC-UV) and gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in Table 1:

(5) TABLE-US-00001 TABLE 1 Reaction Flow Flow Reaction temper- rate of rate of Conver- Selec- pressure ature reactants hydrogen sion tivity Reactant (Bar) ( C.) (ml/min) (L/hr) (%) (%) DOP 20 80 0.018 1.7 99.98 99.8 10 90 0.018 1.7 99.98 99.7

Embodiment 2

(6) 7 mL of the catalyst B (20-30 mesh size) was filled in a reaction tube and reduced at 450 C. in hydrogen atmosphere. After cooling, the reactor was fed with dibutyl phthalate (DBP) by pump to perform hydrogenation reaction. After the reaction, the products were collected for quantitative measurement. The conversion and selectivity were analyzed by liquid chromatography-UV (LC-UV) and gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in Table 2:

(7) TABLE-US-00002 TABLE 2 Reaction Flow Flow Reaction temper- rate of rate of Conver- Selec- pressure ature reactants hydrogen sion tivity Reactant (Bar) ( C.) (ml/min) (L/hr) (%) (%) DBP 20 70 0.018 1.7 99.96 99.7 10 80 0.018 1.7 99.97 99.7

Embodiment 3

(8) 7 mL of the catalyst B (20-30 mesh size) was filled in a reaction tube and reduced at 450 C. in hydrogen atmosphere. After cooling, the reactor was fed with dibutyl phthalate (DBP) and 1-Butanol (as a solvent), in ratio 1:1 by weight, by pump to perform hydrogenation reaction. After the reaction, the products were collected for quantitative measurement. The conversion and selectivity were analyzed by liquid chromatography-UV (LC-UV) and gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in Table 3:

(9) TABLE-US-00003 TABLE 3 Reaction Flow Flow Reaction temper- rate of rate of Conver- Selec- pressure ature reactants hydrogen sion tivity Reactant (Bar) ( C.) (ml/min) (L/hr) (%) (%) DBP and 1- 20 70 0.042 3.2 99.98 99.6 butanol 10 80 0.042 3.2 99.98 99.4 mixed solution (mix ratio: 1:1 by weight) solution

Embodiment 4

(10) 7 mL of the catalyst B (20-30 mesh size) was filled in a reaction tube and reduced at 450 C. in hydrogen atmosphere. After cooling, the reactor was fed with di(2-ethylhexyl) phthalate (DOP or DEHP) by pump to perform hydrogenation reaction. After the reaction, the products were collected for quantitative measurement. The conversion and selectivity were analyzed by liquid chromatography-UV (LC-UV) and gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in Table 4:

(11) TABLE-US-00004 TABLE 4 Reaction Flow Flow Reaction temper- rate of rate of Conver- Selec- pressure ature reactants hydrogen sion tivity Reactant (Bar) ( C.) (ml/min) (L/hr) (%) (%) DOP 20 70 0.016 1.5 99.99 99.8 10 80 0.016 1.5 99.99 99.7

Embodiment 5

(12) 7 mL of the catalyst B (20-30 mesh size) was filled in a reaction tube and reduced at 450 C. in hydrogen atmosphere. After cooling, the reactor was fed with di(2-ethylhexyl) phthalate (DOP) and 2-ethyl-hexanol (as a solvent), in ratio 1:1 by weight, by pump to perform hydrogenation reaction. After the reaction, the products were collected for quantitative measurement. The conversion and selectivity were analyzed by liquid chromatography-UV (LC-UV) and gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in Table 5:

(13) TABLE-US-00005 TABLE 5 Reaction Flow Flow Reaction temper- rate of rate of Conver- Selec- pressure ature reactants hydrogen sion tivity Reactant (Bar) ( C.) (ml/min) (L/hr) (%) (%) DOP and 2- 20 70 0.039 3.0 99.98 99.7 ethyl- 10 75 0.039 3.0 99.99 99.7 hexanol mixed solution (mix ratio: 1:1 by weight)

Embodiment 6

(14) 7 mL of the catalyst B (20-30 mesh size) was filled in a reaction tube and reduced at 450 C. in hydrogen atmosphere. After cooling, the reactor was fed with di-isononyl phthalate (DINP) by pump to perform hydrogenation reaction. After the reaction, the products were collected for quantitative measurement. The conversion and selectivity were analyzed by liquid chromatography-UV (LC-UV) and gas chromatograph (GC), respectively. The operating conditions and the corresponding results are shown in Table 6:

(15) TABLE-US-00006 TABLE 6 Reaction Flow Flow Reaction temper- rate of rate of Conver- Selec- pressure ature reactants hydrogen sion tivity Reactant (Bar) ( C.) (ml/min) (L/hr) (%) (%) DINP 20 70 0.019 1.7 99.98 99.7 10 80 0.019 1.7 99.99 99.7

Embodiment 7

(16) 7 mL of the catalyst B (20-30 mesh size) was filled in a reaction tube and reduced at 450 C. in hydrogen atmosphere. After cooling, the reactor was fed with di-isononyl phthalate (DINP) and isononyl alcohol (as a solvent), in ratio 1:1 by weight, by pump to perform hydrogenation reaction. After the reaction, the products were collected for quantitative measurement. The conversion and selectivity were analyzed by liquid chromatography-UV (LC-UV) and gas chromatograph (GC). The operating conditions and the corresponding results are shown in Table 7:

(17) TABLE-US-00007 TABLE 7 Reaction Flow Flow Reaction temper- rate of rate of Conver- Selec- pressure ature reactants hydrogen sion tivity Reactant (Bar) ( C.) (ml/min) (L/hr) (%) (%) DINP and 20 70 0.045 4.1 99.99 99.8 isononyl 10 80 0.045 4.1 99.99 99.7 alcohol mixed solution (mix ratio: 1:1)