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A vailable online at www.sciencedirect.com Chemical Engineering and Processing 47 (2008) 787–792 Development of an anthraquinoneg , Universit y of Pittsburgh, Pittsburgh, PA 15261, USA. Tel.: +1 412 383 9 4 9 4 ; f a x : + 1 4 1 2 6 2 4 9 6 3 9. E-mail address: qunlai@gmail.com . 0255-2701/$ – see front matter © 2007 Elsevier B.V. All rights reserved. doi: 10.1016/j.cep.2006.12.012 40 hydrogen peroxide plants had been constructed and suc- cessfully started up at home and abroad with the single-plant capacities ranging from several thousands m.t./year to over 40,000 m.t./year [2] . The chemical principle and schematic dia- gram of the AO process developed by LRICI are shown in Figs. 1 and 2 , respectively [3] . This AO process has the following features [3–5] : 1. 2-Ethylanthraquinone (EAQ, 1 ) is dissolved in a solvent mix- ture of C –C aromatics and trioctylphosphate (TOP) to form a working solution (WS). 2. A trickle bed is used as the hydrogenation reactor where EAQ is hydrogenated over a Pd/Al O catalyst to form 2-ethylanthrahydroquinone (EAQH , 2 ); at the same time, small amount of EAQH can be further hydrogenated to form 2-ethyl-5,6,7,8-tetrahydroanthrahydroquinone (H EAQH , 4 ). 3. A bubble column is used as the oxidation reactor where EAQH and H EAQH are oxidized by air to generate hydrogen peroxide and their corresponded EAQ and 2-ethyl- 5,6,7,8-tetrahydroanthraquinone (H EAQ, 3 ). 4. A sieve-plate extraction tower is used to extract generated hydrogen peroxide by deionized water. " id="pdf-obj-0-2" src="pdf-obj-0-2.jpg">

Available online at www.sciencedirect.com

A vailable online at www.sciencedirect.com Chemical Engineering and Processing 47 (2008) 787–792 Development of an anthraquinoneg , Universit y of Pittsburgh, Pittsburgh, PA 15261, USA. Tel.: +1 412 383 9 4 9 4 ; f a x : + 1 4 1 2 6 2 4 9 6 3 9. E-mail address: qunlai@gmail.com . 0255-2701/$ – see front matter © 2007 Elsevier B.V. All rights reserved. doi: 10.1016/j.cep.2006.12.012 40 hydrogen peroxide plants had been constructed and suc- cessfully started up at home and abroad with the single-plant capacities ranging from several thousands m.t./year to over 40,000 m.t./year [2] . The chemical principle and schematic dia- gram of the AO process developed by LRICI are shown in Figs. 1 and 2 , respectively [3] . This AO process has the following features [3–5] : 1. 2-Ethylanthraquinone (EAQ, 1 ) is dissolved in a solvent mix- ture of C –C aromatics and trioctylphosphate (TOP) to form a working solution (WS). 2. A trickle bed is used as the hydrogenation reactor where EAQ is hydrogenated over a Pd/Al O catalyst to form 2-ethylanthrahydroquinone (EAQH , 2 ); at the same time, small amount of EAQH can be further hydrogenated to form 2-ethyl-5,6,7,8-tetrahydroanthrahydroquinone (H EAQH , 4 ). 3. A bubble column is used as the oxidation reactor where EAQH and H EAQH are oxidized by air to generate hydrogen peroxide and their corresponded EAQ and 2-ethyl- 5,6,7,8-tetrahydroanthraquinone (H EAQ, 3 ). 4. A sieve-plate extraction tower is used to extract generated hydrogen peroxide by deionized water. " id="pdf-obj-0-7" src="pdf-obj-0-7.jpg">

Chemical Engineering and Processing 47 (2008) 787–792

A vailable online at www.sciencedirect.com Chemical Engineering and Processing 47 (2008) 787–792 Development of an anthraquinoneg , Universit y of Pittsburgh, Pittsburgh, PA 15261, USA. Tel.: +1 412 383 9 4 9 4 ; f a x : + 1 4 1 2 6 2 4 9 6 3 9. E-mail address: qunlai@gmail.com . 0255-2701/$ – see front matter © 2007 Elsevier B.V. All rights reserved. doi: 10.1016/j.cep.2006.12.012 40 hydrogen peroxide plants had been constructed and suc- cessfully started up at home and abroad with the single-plant capacities ranging from several thousands m.t./year to over 40,000 m.t./year [2] . The chemical principle and schematic dia- gram of the AO process developed by LRICI are shown in Figs. 1 and 2 , respectively [3] . This AO process has the following features [3–5] : 1. 2-Ethylanthraquinone (EAQ, 1 ) is dissolved in a solvent mix- ture of C –C aromatics and trioctylphosphate (TOP) to form a working solution (WS). 2. A trickle bed is used as the hydrogenation reactor where EAQ is hydrogenated over a Pd/Al O catalyst to form 2-ethylanthrahydroquinone (EAQH , 2 ); at the same time, small amount of EAQH can be further hydrogenated to form 2-ethyl-5,6,7,8-tetrahydroanthrahydroquinone (H EAQH , 4 ). 3. A bubble column is used as the oxidation reactor where EAQH and H EAQH are oxidized by air to generate hydrogen peroxide and their corresponded EAQ and 2-ethyl- 5,6,7,8-tetrahydroanthraquinone (H EAQ, 3 ). 4. A sieve-plate extraction tower is used to extract generated hydrogen peroxide by deionized water. " id="pdf-obj-0-11" src="pdf-obj-0-11.jpg">

Development of an anthraquinone process for the production of hydrogen peroxide in a trickle bed reactor—From bench scale to industrial scale

Qunlai Chen

Liming Research Institute of Chemical Industry, Luoyang, Henan 471001, PR China

Received 9 July 2006; received in revised form 28 December 2006; accepted 28 December 2006 Available online 30 January 2007

Abstract

This paper discusses the development of an anthraquinone auto-oxidation (AO) process for the production of hydrogen peroxide with the focus on its key step—liquid-phase hydrogenation of active anthraquinones over Pd/Al 2 O 3 catalyst. The main issues considered in the process development were the selection of a trickle bed as the hydrogenation reactor, the degradation of active anthraquinones and regeneration of their degradation by- products, the development of a new spherical Pd/Al 2 O 3 hydrogenation catalyst, its deactivation and regeneration, and the examination of its activity, selectivity, life, etc. The establishment of start-up and normal operational procedures ensured minimum degradation of active anthraquinones and maximum stable operation. The experimental results from bench and pilot tests paved the way toward industrial production of hydrogen peroxide. © 2007 Elsevier B.V. All rights reserved.

Keywords: Hydrogen peroxide; Anthraquinone process; Hydrogenation; Pd/Al 2 O 3 catalyst; Trickle bed; Bench and pilot test

1. Introduction

Hydrogen peroxide (H 2 O 2 ) is a green chemical since its decomposition generates only water and oxygen. It is widely used as a bleaching agent in pulp and paper manufacture, as a green oxidant in various organic, inorganic syntheses, etc. The dominating technology in producing hydrogen peroxide is anthraquinone auto-oxidation (AO) process. In this process, 2- alkylanthraquinone is sequentially hydrogenated and oxidized in different reactors to generate hydrogen peroxide. The alkyl group in 2-alkylanthraquinone can be ethyl, propyl, butyl or amyl, etc. As strong demand drove capacity growth at the rate of 19% per year in the past decade, China became world’s largest hydrogen peroxide producer at the end of 2004 [1]. Currently, total hydrogen peroxide capacity in China is about 700,000 metric tonnes (m.t.)/year (as 100% H 2 O 2 ) [2]. Liming Research Institute of Chemical Industry of China (LRICI) has been engaging in developing the AO process for over 30 years. Using the technology developed by LRICI, over

Current address: 1249 Benedum Hall, Department of Chemical and Petroleum Engineering, University of Pittsburgh, Pittsburgh, PA 15261, USA. Tel.: +1 412 383 9494; fax: +1 412 624 9639. E-mail address: qunlai@gmail.com.

0255-2701/$ – see front matter © 2007 Elsevier B.V. All rights reserved.

doi:10.1016/j.cep.2006.12.012

40 hydrogen peroxide plants had been constructed and suc- cessfully started up at home and abroad with the single-plant capacities ranging from several thousands m.t./year to over 40,000 m.t./year [2]. The chemical principle and schematic dia- gram of the AO process developed by LRICI are shown in Figs. 1 and 2, respectively [3]. This AO process has the following features [3–5]:

  • 1. 2-Ethylanthraquinone (EAQ, 1) is dissolved in a solvent mix- ture of C 9 –C 10 aromatics and trioctylphosphate (TOP) to form a working solution (WS).

  • 2. A trickle bed is used as the hydrogenation reactor where EAQ is hydrogenated over a Pd/Al 2 O 3 catalyst to form 2-ethylanthrahydroquinone (EAQH 2 , 2); at the same time, small amount of EAQH 2 can be further hydrogenated to form 2-ethyl-5,6,7,8-tetrahydroanthrahydroquinone (H 4 EAQH 2 , 4).

  • 3. A bubble column is used as the oxidation reactor where EAQH 2 and H 4 EAQH 2 are oxidized by air to generate hydrogen peroxide and their corresponded EAQ and 2-ethyl- 5,6,7,8-tetrahydroanthraquinone (H 4 EAQ, 3).

  • 4. A sieve-plate extraction tower is used to extract generated hydrogen peroxide by deionized water.

  • 788 Q. Chen / Chemical Engineering and Processing 47 (2008) 787–792

788 Q. Chen / Chemical Engineering and Processing 47 (2008) 787–792 Fig. 1. Chemical principle of

Fig. 1. Chemical principle of AO process for the production of hydrogen per- oxide.

  • 5. The crude hydrogen peroxide obtained is then evaporated and distilled in purification and concentration steps to obtain final product (see [3] for details).

  • 6. The working solution from the extraction tower is treated in a post-treatment step and then circulated back to the hydro- genation reactor.

This paper discusses the most important issues encoun- tered during the development of LRICI’s industrial AO process with the focus on the key step—hydrogenation of active anthraquinones. These include the selection of a trickle bed as the hydrogenation reactor, the degradation of EAQ and H 4 EAQ and regeneration of their degradation by-products, the prepara- tion of a new Pd/Al 2 O 3 hydrogenation catalyst, its deactivation and regeneration, and the pilot experiment in order to determine catalyst activity, selectivity, life, etc.

  • 2. Development of the AO process

    • 2.1. Selection and modeling of the hydrogenation reactor

The AO process involves two major chemical reactions:

hydrogenation of active anthraquinones and oxidation of their corresponded anthrahydroquinones. The hydrogenation of EAQ and H 4 EAQ is the key step in developing the AO process due to its complicated reaction mechanism and inevitable side reactions (while the oxidation of EAQH 2 and H 4 EAQH 2 by air

788 Q. Chen / Chemical Engineering and Processing 47 (2008) 787–792 Fig. 1. Chemical principle of

Fig. 2. Schematic diagram of AO process for the production of hydrogen per- oxide.

is easy to conduct even without using any catalyst). The hydro- genation of EAQ and H 4 EAQ is carried out in a three-phase reactor under mild reaction conditions (T 80 C, P 5 bar). In this reaction system, gas phase is hydrogen, liquid phase is the working solution, and solid phase is the hydrogenation catalyst. Three types of hydrogenation reactors were tested in a bench plant: a slurry stirring tank, a trickle bed and a slurry bubble column. In order to obtain accurate information, this bench plant was designed to contain all the main steps listed in Fig. 2. The highlights of three hydrogenation reactors examined in this study are listed in Table 1. Although slurry stirring tank was initially studied and several demonstration plants were built with the capacities of several thousands m.t./year, it was still eliminated when LRICI tried to develop large scale industrial plant due to its drawbacks listed in Table 1 and the difficulty to scale up. Slurry bubble col- umn was simple in structure, but its application was limited by its complicated backwashable filtration system (any leakage of hydrogenation catalyst to the oxidation step could be a disaster since palladium had strong ability to catalyze the decomposition of hydrogen peroxide) and the difficulty in developing a powder catalyst with strong mechanical strength (a pilot plant with slurry bubble column as the hydrogenation reactor was just success- fully developed recently by LRICI [7]). Therefore, trickle bed was selected as the hydrogenation reactor for pilot test. Although the hydrogenation activity of tested catalyst was relatively low. Intrinsic kinetics for the hydrogenation of EAQ and H 4 EAQ are very important toward the development of AO process, sev- eral papers had been published on this subject. In general, the hydrogenation reaction rate is first order with respect to hydro- gen partial pressure and zero order with respect to EAQ and H 4 EAQ concentration. Chen [8] reviewed these publications and recommended the following rate expressions for the hydrogena- tion of EAQ and H 4 EAQ in a stirring slurry reactor excluding any mass transfer resistance. These recommended expressions were successfully used in the modeling of trickle bed hydrogenation reactors [9,10]:

r EAQH 2 = 65.58 exp

17, 041

RT

P H 2

r H 4 EAQH 2 = 2.62 exp

10, 629

RT

P H 2

(1)

(2)

In the earlier studies, an experimental statistical model was also developed to model the performance of Pd/Al 2 O 3 catalyst in the trickle bed reactor. This model can be expressed by the following equation [11]:

R app = A 0 exp

B 1

T

t B 2 P

B 3

H 2

LHSV B 4 GHSV B 5 (3)

By using least square method, parameters in Eq. (3) were regressed from the experimental data. Their results are given in Table 2. Several conclusions could be drawn from this experimen- tal model: (1) the limitation step in this process was not the chemical reaction because of low apparent reaction activation energy obtained from regression, it was most likely the internal

Q. Chen / Chemical Engineering and Processing 47 (2008) 787–792

Table 1 Highlights of three hydrogenation reactors examined in bench experiments

789

Item

Slurry stirring tank

Trickle bed

Slurry bubble column

Catalyst

Raney nickel; 30–50 mesh for Ni–Al alloy;

9gH 2 O 2 /L of

WS

0.3

± 0.02%Pd/Al 2 O 3 ;

(1–2)%Pd/Al 2 O 3 –SiO 2 ; powder, expensive

Hydrogenation activity

easy to prepare; self-ignition

extrudate; 3 mm in diameter 6–7 g H 2 O 2 /L WS [6]

10 g H 2 O 2 /L WS

Selectivity

Acceptable selectivity

High selectivity

High selectivity

Filtration

Inside back-washable primary filters; outside safety filter

Safety filter

Outside back-washable primary filters; safety filter

Structure

Complicated structure; carefully designed mechanical stirrer and seal

Simple structure; gas and liquid distributors

Simple structure; gas distributor

Operation

Continuous; high cost; difficult to operate

Continuous; low cost; easy to operate

Continuous; moderate cost; relatively easy to operate

diffusion since, in the experimental range, the change of liquid hourly space velocity (LHSV) and gas hourly space velocity (GHSV) had little effect on apparent reaction rate or catalyst productivity (R app , kg(H 2 O 2 )/[kg(Pd) day]); (2) apparent reac- tion order with respect to hydrogen partial pressure (P H 2 ) was slightly higher than 1, while intrinsic kinetics study showed first order with respect to hydrogen partial pressure; (3) the exponen- tial value B 2 of catalyst age (t) reflected the deactivation feature of Pd/Al 2 O 3 catalyst used in this experiment.

2.2. Degradation of active anthraquinones and regeneration of their degradation by-products

The AO process is unique compared with other hydrogena- tion process in that the reactant, EAQ, in the working solution has to be sequentially hydrogenated and oxidized in order to produce hydrogen peroxide continuously. This continuous circu- lation of EAQ in the working solution requires that the selectivity of hydrogenation catalyst should be as close to unit as possi- ble. The importance of this requirement can be explained as follows. The initial EAQ content in the working solution is in the range of 120–150 g/L, if catalyst selectivity is considered to be 99%, after each circulation, 1% of EAQ in the work- ing solution will be degraded to inert anthraquinone derivatives (this process is called degradation, the formed derivatives are called degradation by-products) which lose the ability to gen- erate hydrogen peroxide. If there is no addition of fresh EAQ and no regeneration of degradation by-products, after 100 circu- lations (about several weeks’ operation), about 75–95 g/L EAQ will be converted to the degradation by-products. This is obvi- ously unacceptable in industrial practice. Thus, apart from the necessity to develop a new Pd/Al 2 O 3 hydrogenation catalyst with high activity and well above 99% selectivity, understanding

Table 2 Parameters in Eq. (3) regressed from experimental results

A

0

B

1

B

2

B

3

B

4

B

5

277839.81

1755.69

0.3938

1.1527

0.0775

0.0049

the degradation mechanism and developing some proper meth- ods to regenerate these degradation by-products became one of the priority issues in developing industrial AO process. During the hydrogenation of EAQ, small amount of EAQ can be further hydrogenated to form H 4 EAQH 2 , which is then oxidized to generate H 4 EAQ as shown in Fig. 1. H 4 EAQ was initially considered as a degradation by-product. However, lat- ter study showed that H 4 EAQ could also be hydrogenated and oxidized to generate hydrogen peroxide. Furthermore, the for- mation of large amount of H 4 EAQ in working solution benefited the AO process in that [12,13]: (1) the presence of H 4 EAQ could increase the total solubility of EAQ and H 4 EAQ in solvents; (2) the hydrogenation of H 4 EAQ was faster than that of EAQ; (3) the degradation of H 4 EAQH 2 was slower than that of EAQH 2 . At present, H 4 EAQ is no longer considered as a degradation by-product. The degradation of active anthraquinones (including EAQ and H 4 EAQ) can be generally divided into hydrogenation degra- dation (which can be further divided into the deep hydrogenation of aromatic ring and the hydrolysis of carbonyl group in active anthraquinones) and oxidation degradation. The major identified degradation by-products formed during hydrogena- tion were hydroxyanthrones and anthrones of EAQ, H 4 EAQ, etc. [12–14]. Although the mechanism of the hydrogenation degradation is complicated, it is mainly caused by the deep hydrogenation. Experimental results suggested that the follow- ing measures could be used to decrease the formation of the degradation by-products [13]: (1) to keep lower hydrogena- tion extent (which was defined as the ratio of hydrogenated anthraquinones over active anthraquinones; <70%) by using higher active anthraquinones content in the working solution (for example, the preferred active anthraquinones content in the working solution should be in the range of 120–150 g/L); (2) to keep the weak basicity of the working solution in order to prevent the equilibrium of active anthraquinones and their cor- responded hydroxyanthrones from shifting to hydroxyanthrones [15]; (3) to keep higher H 4 EAQ content in the working solution in order to ensure only H 4 EAQ was hydrogenated in the trickle bed reactor since the following equilibrium reaction completely shifted to right [16] under reaction conditions:

EAQH 2 + H 4 EAQ EAQ + H 4 EAQH 2 (4)

  • 790 Q. Chen / Chemical Engineering and Processing 47 (2008) 787–792

Table 3 Regeneration results of degradation by-products in the working solution

Regeneration agent

Time (h)

T ( C)

Increased amount (g/L)

 

EAQ

H 4 EAQ

Alkaline alumina

3

50

6.2

9.2

3

60

12.0

10.3

3

80

17.4

18.8

Acid

1

50

5.0

39.2

1

70

3.8

44.4

Base

1

50

5.5

17.9

1

60

5.5

40.5

Peroxide

4

50

5.2

21.0

4

60

5.4

27.2

The oxidation degradation was relatively simple and formed only H 4 EAQ-11,12-epoxide. This epoxide could be easily regenerated back to H 4 EAQ by alkaline alumina. Several regeneration agents had been developed to regenerate these degradation by-products, these included alkaline alumina, acid, base, peroxide, etc.; their regeneration abilities are given in Table 3 [13]. Although the regeneration ability of alkaline alumina was not as strong as that of other agents, it could be easily incorporated into the AO process as an online generation method. A detailed discussion on specifications of the alkaline alumina, the method used to measure its regeneration ability and the operational conditions can be found in [17]. However, even with the online regeneration, the working solution still contained some degradation by-products after certain period of operation. Therefore, certain amount of working solution should be withdrawn from plant and be treated with other agents listed in Table 3.

2.3. Development of a new hydrogenation catalyst, its deactivation and regeneration

As can be seen from above discussion, the hydrogenation activity of extruded Pd/Al 2 O 3 was relatively low. In order to economically produce hydrogen peroxide in the industrial scale, it is necessary to develop a new hydrogenation catalyst which should have both high activity and high selectivity. The initial focus was on the development of a suitable Al 2 O 3 support and a proper deposition method to impregnate palladium on the sup- port. Experimental results showed that many parameters had influence on catalytic activity and selectivity; these included surface area, pore volume and pore size distribution, crystal form of support, palladium dispersion, thickness of palladium layer, calcination temperature, etc. A new palladium catalyst was developed by manipulating these parameters. Some properties of this new spherical Pd/Al 2 O 3 catalyst, old extruded catalyst and a commercial catalyst [18] are listed in Table 4. As can be seen the new Pd/Al 2 O 3 catalyst had several significant advantages over other catalysts: 50–60% higher in productivity, 20–30% lighter in bulk density, 10–20% less in palladium content and 15–20% smaller in diameter. The bench and pilot tests showed that, under similar selectivity, its hydrogenation activity was about 30–40%

Table 4 Selected properties of different hydrogenation catalysts in the AO process

Catalyst

New Pd

Old Pd

Compared

catalyst [20]

catalyst

catalyst [18]

Shape Support

Sphere Al 2 O 3

Extrudate Al 2 O 3

Sphere Al 2 O 3

Diameter (mm)

2–3

3

2.5–3.5

Pd content (%)

0.25–0.3

0.28–0.32

0.28–0.32

Bulk density (kg/L)

0.45–0.55

0.6–0.7

0.6

Productivity (kg(H 2 O 2 )/ [kg(Pd) day])

1600

1000

1100

higher than that of the old palladium catalyst. This significant

improvement in catalyst performance and reduction in particle size and palladium content made the new Pd/Al 2 O 3 hydrogena- tion catalyst a very competitive one in industrializing the AO process since the consumption of this new catalyst was only half of the previous one. The effects of operational parameters on the catalyst performance were given in [19]. The deactivation of Pd/Al 2 O 3 catalyst in the AO process was mainly caused by poisoning and fouling. The impurities which could poison Pd/Al 2 O 3 catalyst in the AO process were carbon monoxide, chlorides, sulfur compounds, some heavy metals, etc. They were mainly from raw materials like hydrogen, C 9 –C 10 aromatics, TOP, EAQ, etc. Maximum contents of these impuri- ties in each raw material were given in [21] in order to protect Pd/Al 2 O 3 catalyst from being poisoned. For example, carbon monoxide content in hydrogen should be less than 10 ppm, sul- fur content in C 9 –C 10 aromatics be less than 5 ppm, etc. Because of the strict control on raw materials, this poisoning was not the main reason for catalyst to lose its activity unless there was a sudden increase in carbon monoxide in hydrogen from pressure swing adsorption (PSA). The major reason in catalyst deactiva- tion was fouling. As the hydrogenation reaction kept running, active anthraquinones and their degradation by-products could precipitate on Pd/Al 2 O 3 catalyst surface to clog catalyst parti- cles, plug pores and block active surface. This fouling led to the decrease in activity and significant increase in pressure drop. The development of regeneration method was focused on removing these precipitations. The regeneration procedure developed had the following steps: treatment of deactivated cat- alyst with a solvent, followed by stripping, and drying with an inert gas. With this treatment, the recovered catalyst activity was in the range of 90–100% of its original activity and its selectivity was usually the same as or even better than that of fresh catalyst.

  • 2.4. Pilot test and industrialization

Pilot test was conducted in a pilot plant shown in Fig. 3, which is similar to that given by Hu [22] and Zheng [23], and the industrial plant had the similar arrangement. When designing and operating this pilot plant, following issues were considered and examined:

(1) Distribution of hydrogen and the working solution: since both hydrogen gas and liquid working solution flowed con- currently down through the catalyst, it was very important

Q. Chen / Chemical Engineering and Processing 47 (2008) 787–792

791

Q. Chen / Chemical Engineering and Processing 47 (2008) 787–792 791 Fig. 3. Flow sheet of

Fig. 3. Flow sheet of the pilot AO process.

to properly design gas and liquid distributors to ensure even distribution of both hydrogen and the working solution in order to prevent the formation of hotspot, where the degrada- tion of active anthraquinones could be greatly accelerated due to the undesired deep hydrogenation. In some cases, part of the hydrogenated working solution was re-circulated back to the hydrogenation reactor to reduce the possibility of hotspot formation. (2) Regeneration of the degradation by-products: two alumina beds were installed in this pilot plant, the first one was located behind the hydrogenation reactor to allow part of the hydrogenated working solution to go through it; the second one was located after dryer which allowed all work- ing solution to go through it. This arrangement ensured the effective regeneration of both hydrogenation and oxidation degradation by-products. (3) A dryer was designed to remove water and some of the water-soluble degradation by-products from the working solution prior to its circulation back to the hydrogenation reactor, to adjust the pH value of the working solution from the weak acidity to the weak basicity in order to decrease hydrogenation degradation. (4) The establishment of start-up and normal operational pro- cedures and the optimization of operational parameters:

as can be seen in Fig. 4, the hydrogenation of active anthraquinones for the production of hydrogen peroxide is quite different from general hydrogenation process. For gen- eral hydrogenation process, since operational temperature and pressure are kept constant during the operation time, cat- alyst activity gradually decreases along with the operation time until it reaches its minimum values; then deactivated catalyst is regenerated to recover its activity. This procedure is repeated until the catalyst activity cannot be recovered economically as shown in Fig. 4(a). While for the AO pro- cess, the initial temperature and pressure were even below their minimum values in order to keep low catalyst activ- ity during the start-up. This could effectively decrease the formation of the degradation by-products. Under these con- ditions, EAQ was gradually converted to H 4 EAQ until the H 4 EAQ content reached the desired level. The corresponded

Q. Chen / Chemical Engineering and Processing 47 (2008) 787–792 791 Fig. 3. Flow sheet of

Fig. 4. Catalyst performance for different hydrogenation processes.

operation time (it could be several weeks) was observed as t 0 in Fig. 4(b). After that, the pilot plant entered the normal operational period: the operational pressure and temperature were gradually increased in order to keep catalyst activ- ity relatively stable until they both reached their maximum values (T max 80 C and P max 5 bar) and the decrease in catalyst activity was observed. Then, Pd/Al 2 O 3 catalyst was regenerated to recover its activity. An online regeneration method based on the results from the bench test was devel- oped to regenerate deactivated catalyst. The regeneration result in the pilot plant was similar to that obtained in the bench test. (5) Catalyst life and raw material consumptions were obtained based on the results obtained from long-term operation (sev- eral years). The experimental results from the pilot test showed that the new Pd/Al 2 O 3 hydrogenation catalyst could be used for 3–4 years without significant loss in activity and selectivity.

According to the experimental results obtained in both bench and pilot tests, the technology using the AO process to industri- ally produce hydrogen peroxide was developed and transferred to over 40 companies at home and abroad [2,3,5]. These indus- trial plants had single-plant capacities ranging from several thousands m.t./year to 40,000 m.t./year, while the dimensions of the hydrogenation reactors were in the range of less than 1 m to several meters in diameter.

3. Conclusions

By experimentally comparing with a slurry stirring tank and a slurry bubble column, a trickle bed was selected as the hydro- genation reactor in the production of hydrogen peroxide via the AO process. An experimental statistical model was developed to correlate the apparent reaction rate or the catalyst productivity with various operational parameters. The experimental study on the degradation of active anthraquinones (including EAQ and

  • 792 Q. Chen / Chemical Engineering and Processing 47 (2008) 787–792

H 4 EAQ) showed that their degradation could be divided into hydrogenation degradation and oxidation degradation. Several regeneration methods were developed to regenerate their degra- dation by-products with alkaline alumina being used as an online regeneration agent and others being used as offline regenera- tion agents. A new spherical Pd/Al 2 O 3 catalyst was prepared with high activity and high selectivity, and its life and consump- tion were examined in a pilot plant. The regeneration method developed for the deactivated catalyst recovered 90–100% of its original activity and completely recovered its selectivity. Experimental results from the pilot test showed that at the start- up period, hydrogenation activity should be kept at a relative low level to allow the gradual formation of H 4 EAQ in order to prevent significant degradation of active anthraquinones. During normal operation, the hydrogenation temperature and pressure were gradually increased to keep hydrogenation activity stable.

Acknowledgment

I would like to dedicate this paper to Professor Changcheng Hu, the founder of anthraquinone auto-oxidation (AO) process in China, of Liming Research Institute of Chemical Industry of China.

References

[1] China becomes world’s largest hydrogen peroxide producer, Chem. Week 166 (41) (2004) 29. [2] Q. Chen, Booming hydrogen peroxide industry in China, China Chem. Reporter 17 (12) (2006) 1920. [3] Q. Chen, Toward cleaner production of hydrogen peroxide in China, J. Clean. Prod. 14 (2006) 708–712. [4] Introduction to the production of hydrogen peroxide by anthraquinone process, www.lrici.com. [5] Q. Chen, Production and application of hydrogen peroxide in China, Mod. Chem. Ind. 21 (1) (2001) 11–14. [6] X. Hu, Regeneration of Pd catalyst in fixed bed, Inorg. Chem. Ind. 30 (5) (1998) 31–32.

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