EH2207N

DESIGN PROJECT I (SEPTEMBER 2015)

PRODUCTION OF 50, 000 METRIC TONNES OF TETRAHYDROFURAN PER

YEAR

CHAPTER 1: PROCESS BACKGROUND AND SELECTION

GROUP MEMBERS

MUHAMMAD FAWWAZ AFIQ BIN MOHD ZAINUDDIN 2013600508

MOHAMAD ALIF BIN MOHD RADZUAN 2013411196
MUHAMMAD KHAIRI BIN TAJURUS 2013233736
MUHAMMAD IDHAM BIN REZALI 2013811872
MOHAMAD HAZRUL BIN TAIB 2013674906
SITI SARAH BINTI AZMI 2013464376

SUPERVISOR:

PUAN NURHASLINA CHE RADZI

FACULTY OF CHEMICAL ENGINEERING

UNIVERSITI TEKNOLOGI MARA

SHAH ALAM
 TABLE OF CONTENTS

CHAPTER 1 1.1 Introduction 1

1.2 Physical, Chemical And Physiological Properties 2
1.2.1 Physical Properties of THF 2
1.2.2 Chemical Properties of THF 4
1.2.3 Physiological Properties of THF 4
1.3 Tetrahydrofuran Uses And Application 4
1.4 Process Selection 7
1.4.1 Acetylene Based Process (Reppe
7
Technology)
1.4.1.1 Process details of THF production
8
using Reppe Technology
1.4.2 Maleic Anhydride Based Process (Davy
9
Technology)
1.4.2.1 Process details of THF production
10
by Davy technology
1.4.2.1 Alternative feedstock for Davy
12
a technology
1.4.3 Furfural Based Process (Biomass) 14
1.4.3.1 Process details of THF production
14
by Furfural
1.5 Weightage Scoring Analysis 15
1.5.1 Raw Material 15
1.5.2 Product Selectivity 16
1.5.3 Safety Factor 16
1.5.4 Operating Condition and Energy
16
Consumption
1.5.5 Catalyst 16
1.5.6 Economic Value 17
1.5.7 Purity 17
1.5.8 Weightage Scoring 17
 TABLE OF CONTENTS

1.5.9 Conclusion of Scoring Method 20

1.6 Production Of THF Via DAVY Technology 20
1.6.1 Chemistry 20
1.6.2 THF Plant Process Flow Diagram 22
1.6.3 THF Plant Process Description 23
1.6.4 Process Equipment 28
1.7 Conclusion 30
1.8 References 31
 CHAPTER 1

PROCESS BACKGROUND AND SELECTION

1.1 INTRODUCTION

Tetrahydrofuran (THF) is cyclic ether and widely utilized in diverse industrial

applications. It is mainly used in the production of poly-tetra-methylene glycol (PTMEG).
It is also used as a solvent in many applications including production of polyvinyl chloride
(PVC), magnetic films and in Grignard reactions (Hunter et al., 2006). The IUPAC name
of THF is Oxacyclopentane. The other names are 1, 4-epoxybutane, butylene oxide,
cyclotetramethylene oxide, oxacyclopentane and diethylene oxide.

In industry, it is primarily used as a solvent for numerous polymers and resins. It

also has extensive uses in the production of rubber, cellophane, adhesives, magnetic
tape and printing inks. Under strongly acidic conditions, THF polymerizes to form
Polytetramethylene Ether Glycol (PTMEG), which is utilized in the manufacture of
various flexible and elastic fibers. THF is also present in the adhesives used to join
plastic pipes for well construction and water treatment systems, and since THF is a
component of food packaging adhesives, it can be an indirect food additive. It is also
frequently used as a solvent in numerous pharmaceutical synthesis procedures.

Figure 1.0 Structure of Tetrahydrofuran

(Source: https://en.wikipedia.org/wiki/Tetrahydrofuran)

1
1.2 PHYSICAL, CHEMICAL AND PHYSIOLOGICAL PROPERTIES

1.2.1 Physical Properties of THF

According to P. Dreyfuss, THF is a volatile solvent that miscible with water and common
organic solvents. It only required protective clothing and adequate ventilation during
handling, similar as handling volatile organic compound. In order to avoid splashing,
goggles should be worn instead. Furthermore, as THF is classified as flammable liquid,
handling precautions and cares are essential to avoid fire hazard incidents. For storage
purpose, it is best to be stored and handled in common steel tanks and piping. Welded
piping is recommended rather than screwed fitting due to the excellent properties of THF
as describe in Table 1.0. Besides, pump and valve packing must be tight and non-
soluble.

Table 1.0: Physical properties of Tetrahydrofuran (THF)

Property Value
Molecular weight 72.108
Boiling point (at 760 mm Hg), ºC 66
Freezing point, ºC -108.5
Vapor pressure, 20ºC, mm Hg 143
kPa 19.1
Density-liquid, 20ºC, g/ml (Mg/m3) 0.888
vapor (air = 1) 2.49
Viscosity, 20ºC, cP (mPa.s) 0.48
Surface tension in air, 25ºC, dyn/cm (mN/m) 26.4
Refractive index 1.4073
Heat of vaporization (at bp), cal/g 95
kJ/kg 397
Heat of combustion, kcal/mol 597
Mj/kg 34.6

2
Table 1.0: Physical properties of Tetrahydrofuran (THF) (continued)

Property Value
Specific heat, liquid,
20ºC, cal/g. ºC 0.469
kJ/kg.K 1.962
50ºC, cal/g. ºC 0.469
kJ/kg.K 2.090
Vapor, 66ºC, cal/g. ºC 0.37
kJ/kg.K 1.55
-1
Coefficient of thermal expansion, 10-20ºC, ºC (average) 0.00126
Flash point (TCC), ºC -14.4
Auto-ignition temperature, ºC 321
Flammability limits in air,
25ºC, lower, %vol. THF 2
upper, %vol. THF 11.8
Critical temperature, ºC 268
Critical pressure, atm 51.2
MPa 5.19
Dielectric constant, ϵ, 20ºC 7.54
30ºC 7.25
Conductivity, 25ºC, µ mhos/cm 0.015
µ S/m 1.5
Dipole moment, µ, 25-50ºC, Debye units 1.7
Solubility parameter, (cal/cm3)1/2 9.7
3 1/2
(kJ/dm ) 19.8
Hydrogen bonding index, γ 2.7
Evaporation rate (n-butyl acetate = 1) 8.0
Miscibility: water, esters, ketones, alcohols, diethyl ether;
Infinite
aliphatic, and chlorinated hydrocarbons
Explosion limits (% by volume in air, 25ºC) 1.8-11.8
Hydrogen bonding index, γ 2.7

3
1.2.2 Chemical Properties of THF

THF is saturated cyclic ether and most of its chemical properties are similar to the
aliphatic ethers. Thus, it is inert to sodium or potassium, dilute mineral acids, Grignard
reagents, oxidizing agents and metal hydrides. Moreover, THF can undergo various
chemical reactions such as polymerization, oxygen-replacement, ring-substitution,
hydrolytic-cleavage and molecular-addition reactions unlike linear aliphatic ethers.
However, during storage and transfer, peroxide can form in unstabilized THF. Thus, a
non-volatile antioxidant is added to prevent significant quantities of THF peroxide. An
example of non-volatile antioxidant is 2,6-di.t-butyl-4-methylphenol (butylated
hydroxytoluene) P.Dreyfuss (1982).

1.2.3 Physiological Properties of THF

THF is hazardous to health with respect to toxicity. A prolonged exposure to THF may
cause narcosis, nausea, dizziness and headache. It causes skin irritation and eye
irritation as well. According to the du Pont THF studies for Toxicology and Industrial
Medicine, there is no severe effect in lung, heart, liver, kidney and other organs when
exposed to high concentrations of THF vapors in air. As specified by Occupational
Safety and Health Administration of USA, the threshold limit value (TLV) is 200 ppm. In
addition, if it been swallowed, vomiting should not be prompted as it can cause severe
lung irritation P.Dreyfuss (1982).

1.3 TETRAHYDROFURAN USES AND APPLICATION

THF is an important intermediate in producing numbers of chemicals and plastics. THF

can be produced in many ways and most of them have been patented by the developer.
Famous patented methods in producing THF are such as Davy process, Mitsubishi
process, Reppe and others. In addition, THF is usually produced by multi-step sequence
starting from maleic acid and hydrogen, or Butanediol, with help of alcohol group’s
chemical such as ethanol and methanol in presence of catalyst.

THF is a derivative of Butanediol (BDO) through a dehydration process or can be

produce concurrently with BDO by using Davy Process. According to special report

4
published by Sampat (2011), THF is used widely mainly in plastic industry as a
precursor to polytetrahydrofuran (PETMEG), a component of cast and thermoplastic
polyurethane elastomers, polyurethane stretch fibers, and also high performance
copolymer polyether elastomers. All of these thermoplastic components of PETMEG are
commonly used in industrial and commercial end product from industrial grade tires,
mining screens, transparent film for laminating, medical tubing, fabric and leather
coatings and also artificial leather. As reporting by IHS (2013), in about 79% of THF
usage is focused on supplying the demand of manufacture of PETMEG in order to
produce growing industry of spandex world widely. In Asia, the share of THF is even
higher at 86% to 88% of THF is used to cover the demand for spandex.

THF is virtually dissolves in all plastics with an exception of certain polyamides

and polyfluoroethylene. THF is importantly dissolved in polyvinyl chloride (PVC),
polyethylene, polystyrene, polyesters resin, phenol formaldehyde resins and epoxy
resins. The largest solvent consumption of THF market is used in PVC cements, and
also has been used as a reaction solvent in production of pharmaceuticals, in Grignard
reactions and as chromatographic solvent. In addition, THF’s high volatility and very high
purity facilitate solvent removal and recovery without leaving residues on the products.

THF, also known as tetramethylene oxide or 1, 4-epoxybutane and oxolane, is a

five-membered cyclic ether. THF’s sterically unhindered oxygen atom carries two
unshared pairs of electrons. Two unshared electron pairs are structure for coordination
formation complexes and the other favors the solvation cation. These properties make
THF influence the rate and selectivity of chemical reaction for solvent reagents uses.

5
 Artificial leather

Pharmaceutical intermediates
Polyurethane resin

Construction materials

Polytetramethylene ether glycol

THF Spandex
(PTMEG)

Injection moulding
Thermoplastic polyester
elastomer

(TPEE) resin Thermoplastic urethane

elastomer
Solvent

Figure 1.1 Application and Uses of THF

6
1.4 PROCESS SELECTION

In this design project, the goal is to design THF new chemical plant. Various literatures
have been studied in order to evaluate the significant process of the design. These
processes include Acetylene based process (Reppe), Maleic Anhydride based process
(Davy), and Pentose/Furfural based process. These three major processes are the
crucial parts in designing THF chemical plant. Each of the processes will be compared
and the best technology on production of THF will be selected.

1.4.1 Acetylene Based Process (Reppe Technology)

A process developed by Reppe in the 1930s was for many years the preferred synthetic
route to 1, 4-butanediol and THF, and it is still the most common approach in Europe
and the United States (Ullman, 2011). The Reppe process involves a reaction between
acetylene and formaldehyde to give 2-butyne-1, 4-diol, with subsequent hydrogenation
to 1, 4-butanediol. The saturated diol is very readily cyclized to THF with elimination of
water by acid catalysis above 100°C. Thus, Reppe technology can be divided into three
parts:

i. Reaction of Acetylene and Formaldehyde to form 2-butyne-1, 4-diol (BYD).

ii. Hydrogenation of BYD under high pressure to form 1, 4-butanediol (BDO).
iii. Dehydration of BDO to form THF.

Suitable catalysts include inorganic acids, acidic aluminum silicates, and earth or
rare-earth oxides. Quantitative conversion and a yield of almost 100% can be achieved
in an atmospheric-pressure, continuous process with aluminum oxide as the catalyst
provided the THF is continuously distilled out of the reaction mixture as it forms and pure
1,4-butanediol is fed into the reactor at a rate equal to its rate of consumption. The
amount of conversion per unit amount of catalyst is very high.

Crude BDO can be converted into THF very selectively and with little added energy
by a medium-pressure process (Ullman, 2011).

7
1.4.1.1 Process details of THF production using Reppe Technology

In the manufacture of THF, acetylene is first reacted with 10 to 30% formalin (aqueous
formaldehyde) to form BYD. The reaction takes place at 100°C to 110°C and 5bar to
20bar in the presence of modified copper aceylide (Manufacture of 1,4 –butanediol,
2008). The reaction is conducted in a trickle-column reactor containing the copper
acetylide catalyst with Bi as promoter on SiO2 or magnesium silicate.

Figure 1.2 Reactions of Acetylene and Formalin

The intermediate propargyl alcohol is recycled, together with formaldehyde, to the

reaction. The butyne-diol selectivity amounts to 80% (C2H2) and > 90% (HCHO). In the
second step, 2-butyne-1,4-diol is hydrogenated to 1,4-butanediol.

Figure 1.3 Reaction of Butyne-diol and Hydrogen

The hydrogenation can be conducted in the liquid phase at 70- 100°C and 250-
300 bar in the presence of Raney nickel catalyst. Alternatively, the hydrogenation can
take place in the trickle phase at 180 - 200 °C and 200 bar employing Ni catalysts with
Cu and Cr promoters. The selectivity to 1, 4-butanediol reaches about 95%.

Lastly, BDO will be cyclized to THF by elimination of water at 100°C to 250°C

and at atmospheric pressure with aluminum oxide catalyst. Feed of Crude BDO (99
wt%) could yield almost 100% THF with 98% conversion (Ullman, 2011). Figure 1.4
shows the chemical equation from the raw material to the end product.

Figure 1.4 Overall Reppe Process Reactions

8
For this production of THF plant, part one and two of the Reppy Technology is skipped
by buying BDO as raw material which is readily to be cyclized to THF. Table 1.1
summarized process of the Reppe technology with regards to a few parameters.

Table 1.1 Summary of THF Production Using Reppe Technology

Parameter Reppe
Raw material 1. 1, 4-Butanediol
Reaction and Operating Temperature:
Conditions 100°C-250°C
Pressure:
1 bar–5 bar
State:
Liquid
Yield 100% with Aluminum Oxide catalyst
Catalyst and Price Aluminum Oxide
Number of Unit Operation 1 unit of Reactor
2 units of Distillation Column
1 unit of Evaporator (Concentrator)
2 Heat Exchangers
Safety Consideration No major safety consideration

1.4.2 Maleic Anhydride Based Process (Davy Technology)

Raw materials for production of Tetrahydrofuran from maleic anhydride are solely Maleic
Anhydride (MAH) and hydrogen. According to Global Chemical Price report on maleic
anhydride, the price for domestic maleic anhydride in India is decreasing every year from
2013 till year 2015. Meanwhile, the prices of hydrogen are varies based on quantity and
ways of transportation. These two reactants will react through hydrogenation process to
produce tetrahydrofuran (THF).

The process of THF production from maleic anhydride was introduced by JM

Davy. Apart from THF, Davy technology could make its relative, BDO and gamma
butyrolactone (GBL), in variable ratios which are adjustable according to market need.

9
1.4.2.1 Process details of THF production by Davy technology

According to J.M.Davy, 2014, THF and its derivatives are produced in two stages:

i. Maleic Anhydride (MAH) or Succinic Acid is first esterified to dimethyl maleate

(DMM)/succinate.
ii. Hydrogenolysis converts this intermediate to the crude BDO/THF/GBL product
mix.

In the first stage, MAH is reacted with methanol exothermically to form monomethyl
maleate (MMM) and is further reacted with methanol in the presence of a proprietary
solid catalyst to form DMM. The purpose of the esterification step is to convert the acidic
feed to a non-acidic intermediate ester, which is much easier to convert to THF
compared to an acidic feed. In addition, esterification reaction system removes the
reaction water produced prior to hydrogenolysis, enhancing process efficiency.

Figure 1.5 Reaction of MAH to DMM

DMM is then hydrogenated to dimethyl succinate (DMS) where a series of

reactions converts DMS to GBL.

10
 Figure 1.6 Reactions of DMS to GBL

Subsequent conversion of GBL to butanediol proceeds by an equilibrium reaction:

Figure 1.7 Reaction of GBL to BDO

Finally, and depending upon the prevailing reaction conditions, BDO will
dehydrate to form Tetrahydrofuran:

Figure 1.8 Reaction of BDO to THF

The products can be extracted according to desired components using

separation process, distillation. By product such as BDO and GBL will be recycle back to
hydrogenation column. The conversion of MAH is 97% with nearly 100% yield of GBL,
THF and BDO (Johnson Matthey Davy technologies butanediol process, 2013). Figure

11
1.9 shows the summarized of Davy technology process while Figure 1.10 shows the
summarized of all the reactions in Davy technology.

Figure 1.9 Davy Mckee process pathway to produce BDO, THF and GBL.

Figure 1.10 Davy Mckee Process Chemical Reactions

1.4.2.1 (a) Alternative feedstock for Davy technology

Attig, Budge, & Pederson states that in Davy technology, Maleic Acid can be used to
substitute MAH. Usage of Methanol can be avoided by hydrogenation of Maleic Acid
over the use of a catalyst comprising Palladium/Rhenium (Pd/Re) on a carbon support.
Table 1.2 shows the summary of process details of THF production using Davy
technology.

12
Table 1.2 Summaries of Process Details of THF Using Davy Technology

Parameter Davy
Raw material 1. Maleic Acid
2. Hydrogen
Reaction and Operating 1. Maleic Acid + Hydrogen Temperature:
Conditions Dimetyhl Succinate 100°C-300°C
2. Dimethyl Succinate + Hydrogen Pressure:
Gamma butyrolactone 10 bar–40 bar
3. Gamma butyrolactone + State:
Hydrogen Gas
1,4-Butanediol
4. Gamma butyrolactone +
Hydrogen
Tetrahydrofuran + Water
5. 1,4-Butanediol
Tetrahydrofuran
+ Water
Yield 90-100%
Catalyst and Price 1. Palladium
2. Rhenium
Number of Unit Operation 1 unit of Reactor
2 units of Distillation Column
2 unit of Flash Drum
4 Heat Exchangers
Safety Consideration 1. Hydrogen is highly flammable and also explosive.
Compressed Hydrogen is also stored in high pressure
vessel which is 200 to 700 bar (5,000 and 10,000 psi).

13
1.4.3 Furfural Based Process (Biomass)

A process develop in 1988 was the least famous process to produce the THF from
furfural. The raw materials used in furfural based process are furfural and hydrogen.
Furfural is commonly produced from acid hydrolysis of biomass such as corn stalk.

1.4.3.1 Process details of THF production by Furfural

The production of THF by catalytic hydrogenation of furan obtained by furfural

decarbonylation (C. Godawa, 1989). The raw material used in the process is biomass
which is corn stalk. The process was added with palladium catalyst with the presence of
alcohol. Most transformations of furan into tetrahydrofuran use heterogeneous catalyst
processes. Catalysts based on palladium are more favorable for the selective conversion
of furan. Moreover, Gardos and co-workers, who studied the direct transformation of
furfural into THF, obtained only low yields with formation of important quantities of
byproducts using others catalyst.

Hydrogenation of furan is carried out in a discontinuous reactor under agitation at

constant pressure and temperature of 100 ° C. In the process the raw material
undergoes the process to furfural remove to carbon oxide to furan and lastly the
hydrogenation to tetrahydrofuran. The yield is almost 95% (C. Godawa, 1989).

Figure 1.11 Process of Furfural to Furan

Figure 1.12 Process of Furan to Tetrahydrofuran

14
Table 1.3 Summaries of Process Details of THF Using Furfural

Parameter Furfural
Raw material 1. Biomass (Furfural)
2. Hydrogen
Reaction and Operating 1. Furfural Furan+CO2 Temperature:
Conditions 150°C-240°C
2. Furan+H2 THF Pressure:
10 bar–20 bar
State:
Gas
Yield 85%
Catalyst and Price 1. Palladium support with alcohol

Number of Unit Operation Unknown

Safety Consideration 1. Hydrogen is highly flammable and also explosive.
Compressed Hydrogen is also stored in high pressure
vessel which is 350 and 700 bar (5,000 and 10,000 psi).

1.5 WEIGHTAGE SCORING ANALYSIS

In order to find the best route to produce THF, a comparison method calls Weightage
and Scoring method is used. This method provides a systematic approach for selecting
the best process based on many non-monetary criteria. To use this model, basis of
100% weight is used. A score from zero to 100 to each criterion for each process are
assign. After assigning the weights and scores for each process, the weighted score are
calculated by multiplying the weight for each criterion by its score and adding the
resulting values (Turton, 1998). The criteria as follows;

1.5.1 Raw Material

A process with cheaper, long-term available and a less number of raw material can
maintain the profit and the production of the plant. There is an advantage when the raw

15
materials are locally available. Maleic Anhydride in Davy process is the cheapest raw
material compared to the rest. Reppe technology on the other hand has higher cost of
material as compared to Davy technology. The raw material for Pentose/Furfural route is
seasonal and varies according to time. Thus, THF plant might not get a steady source or
flow of raw material.

1.5.2 Product Selectivity

A process with high moles of desired product is more attractive to ensure high
production of the plant. Based on process description mention above, higher selectivity
is attained by using Reppe or Davy technology.

1.5.3 Safety Factor

A safety process is more attractive because it can ensure the plant safety always under
control. It is important to ensure the hazard of the process can be avoided as much as
possible. In order to accomplish the mission, the route with safe operating condition and
environment must be taken into account. As for all the three processes available,
pentose/furfural route provide the safest raw material to be handle rather than the other
two with Reppe process being the second safest process. However, risk assessment is
still needed to be done for all the processes.

1.5.4 Operating Condition and Energy Consumption

Reppe process operates at low pressure, as low as 1 atm. Davy technology on the other
hand operates at mild condition where the condition depends on the catalyst used.
Furfural route operates at high pressure. As comparisons, Reppe process has the safest
operating condition than the other two processes.

1.5.5 Catalyst

All the three processes use difference catalyst requirement to enhance the process.

16
1.5.6 Economic Value

Choosing a process with high economic potential will determine the profitable of the
plant. Furfural route has high cost of investment, thus increase the capital expenses.
Reppe and Davy processes both have low cost of investment.

1.5.7 Purity

Purity of the product is crucial as different purity has its own uses and application. In the
case of tetrahydrofuran, the required purity to be applicable in market is 99-99.99%. All
the processes produce similar purity.

1.5.8 Weightage Scoring

All the critical and main factors are extracted from the process description and are
summarized in Table 1.4. Table 1.5 expressed the weighted scoring method to support
the justification of the selected process. The score use is 0 to 100 which 100 being the
best and 0 being the worst.

17
Table 1.4 Summaries of Processes

Criteria Reppe Technology Davy Technology Furfural

Raw Material Acetylene and Formaldehyde Maleic Anhydride and Hydrogen Pentosan (corn stalk)
Phase Vapor Depend on catalyst but mostly vapor Liquid
Catalyst Aluminum Oxide  Noble metal (e.g: Pd/Re) Palladium supported with
 Copper based (e.g: Cu/SiO2 ) presence of alcohol
Temperature 150°C to 300°C 190°C to 240°C 250-240°C
Pressure 1 bar to 2 bar 10 bar to 40 bar 10 bar to 20 bar
Yield Almost 100% with Aluminium Oxide Almost 100% for any catalyst used Approximately 94% with
catalyst (Ullman, 2011) presence of catalyst
Economic Low investment and suitable for Lower cost of investment and production High cost of investmwnt
Value mass production
Process Mature technology Newer technology than Reppe process Old technology with complex
Demand process
Production Short production process Short production process and high Short production process
efficiency

Purity >99% >99% >99%

18
Table 1.5 Weighted Scoring Analysis

Score Index Total Score

Criteria Factor Weight (%)
Reppe Davy Furfural Reppe Davy Furfural

Raw Material 30 60 99 70 18 29.7 21

Operating
10 99 80 85 9.9 8 8.5
Condition
Catalyst 5 90 80 80 4.5 4 4
Product
10 93 90 85 9.3 9 8.5
Selectivity
Production
10 90 95 75 9.0 9.5 7.5
Capacity
Economic Value 15 70 90 50 10.5 13.5 7.5
Safety Factor 15 90 70 80 13.5 10.5 12
Desired Product
5 99 99 99 4.95 4.95 4.95
and Quality
Total Scoring 100 79.65 89.15 73.95

19
1.5.9 Conclusion of Scoring Method

Based on the weighted score method, Davy process in gas phase has the highest total score as
compared with Reppe process and Furfural route process. Eventhough all processes have their
own justification and advantages but Davy process emphasis more on optimization of unit
operation and economical cost. Davy process uses the cheapest raw materials which result in
much higher profit margin as compare with the other processes. Moreover, due to the reaction
occurred in mind condition, it creates an environmental compatibility. Thus, decision has been
achieved to choose Davy process in gas phase to produce THF.

1.6 PRODUCTION OF THF VIA DAVY TECHNOLOGY

1.6.1 Chemistry

Tetrahydrofuran (THF) is produced by the hydrogenation of Maleic Acid (MA) in the presence of
an acid catalyst. In this THF plant, MA is synthesized first by reacting Maleic Anhydride (MAH)
and water. 100% of the Maleic Anhydride reacts steadily with water to produce MA. The
reaction is as follow:

() ()

The basic THF reactor raw materials are Maleic Acid and Hydrogen. Pd/Re is used as the
catalyst. MA conversion is 100%, where approximately 92.7% of the MA fed to the reactor are
converted to THF and the rest to gamma butyrolactone (GBL). There are 3 reactions occur in
series in the THF reactor. The reactions are,

( ) ( ) ( )

( ) ( ) ( ) ( )

20
( ) ( ) ( ) ( )

21
1.6.2 THF Plant Process Flow Diagram

Figure 1.13 THF Plant Process Flow Diagram

22
1.6.3 THF Plant Process Description

Stream summary table and process flow diagram for the THF process is shown in table 1.6
and figure 1.13 respectively. Raw material for this process is Maleic Anhydride (MAH) and
hydrogen. Firstly, fresh MAH feed enters stream 1 and is fed to R-100, where the MAH
reacts with water from stream 2 to give Maleic Acid (MA). MAH is fed to the THF plant from
MAH storage tank located in the process tank yard. R-100 is basically a vessel where MAH
and water is mixed and steadily reacts to form MA. MA stream is vaporized by E-100, prior
to being sent to packed bed reactor, R-101, THF reactor.

Hydrogen, in stream 6, from Hydrogen storage tank is fed to THF plant in excess at
200 bar. The hydrogen stream is fed to a valve, to decrease the pressure to 1020 kPa. The
stream is then fed to E-101 to be heated to 235°C before entering THF reactor, R-101.

The MA and hydrogen stream are fed to THF reactor, R-101. Inside the reactor, the
MA-Hydrogen mixture is reacted in the presence of Pd/Re catalyst. Typical inlet reaction
temperatures are in the range of 235°C - 275°C. As the reaction temperature does not
exceeded 400°C, the material of construction of the reactor is carbon steel. The reactor
operated at 1 MPa. About 92.7% of the MA fed is converted to THF in the reactor (Ruichao
Zhang et al., 2007). The by-product form in this reaction is GBL and water.

Reactor effluent, containing THF, GBL, MA, Hydrogen and water are sent to E-102
for cooling from 235°C to 40°C. The cooled stream is then fed to V-100 to separate
unreacted hydrogen from the product mixture. The overhead V-100 contains all the
unreacted Hydrogen with a little THF and water carries over. The bottom V-100 contains the
product stream free from Hydrogen.

The bottom stream is then sent to Reactor Column, T-100 where the function is to
separate the THF product from unreacted MA and GBL. The overhead of the Reactor
Column contains about 35.55% THF, 63.47% Water and 0.99% MA. The residue of the
Reactor Column, containing unreacted MA and GBL, are fed back to R-101.

The overhead of Reactor Column containing 33.55% THF, will be purify to

polymerization grade monomer by pressure swing distillation using T-101 and T-102.
Pressure swing distillation is used to break THF/Water azeotrope.

23
 Firstly, the overhead of Reactor Column will enter T-101, Distillation Column. The
column is operated nearly at atmospheric pressure. The overhead of the Distillation Column
contains THF/Water azeotrope at 93.3% THF and 6.7% Water. The residue of the column,
containing water and traces of MA are fed to wastewater treatment plant.

The overhead of T-101, will be pumped to the finishing column, T-102, at 833 kPa.
The column is operated at higher pressure to introduce pressure swing which will break the
THF/water azeotrope. The overhead of the column containing THF and water will be
recycled back to T-101. Polymerization grade THF is produced as the bottom product. The
product specification for THF is less than 200 ppm of water. Then, the THF product is sent
to the product tank.

In the THF process, there are two recovery processes, unreacted MA and GBL
recovery and unreacted Hydrogen recovery. Unreacted MA and GBL are recovered from T-
100 residue. The mixture will then be pumped back to the reactor for further reaction.

For the hydrogen, as the mixture of hydrogen, water and THF emerges from the
overhead of V-100, it will be cool by refrigerant to -18°C and then be fed to the next flash
drum, V-101. In this flash drum, most of THF and water are collected at the bottom and is
fed to T-101 for purification while the overhead contains all the unreacted hydrogen and
traces of THF. The overhead stream is combined with the fresh hydrogen feed which will
then be fed to the THF reactor, R-101.

24
Table 1.6 Stream Summary Table

Stream Number 1 2 3 4 5
o
Temperature ( C) 65.00 133.5 87.08 86.66 235.00
Pressure (kPa) 300.00 300.00 300.00 1050.00 1000.00
Vapor Fraction 0.00 0.00 0.00 0.00 1.00
Mass Flow (kg/h) 8398.00 2000.00 10398.00 10398.00 10398.00
Mole Flow (kmol/h) 85.64 111.00 111.00 111.00 111.00
Component Flow rates
(kmol/h)
Maleic Anhydride 85.6433 0.0000 0.0000 0.0000 0.0000
Water 0.0000 111.00 25.3937 25.3937 25.3937
Maleic Acid 0.0000 0.0000 85.6433 85.6433 85.6433
Hydrogen 0.0000 0.0000 0.0000 0.0000 0.0000
Succinic Acid 0.0000 0.0000 0.0000 0.0000 0.0000
Tetrahydrofuran 0.0000 0.0000 0.0000 0.0000 0.0000
gamma-Butyrolactone 0.0000 0.0000 0.0000 0.0000 0.0000
H(kJ/mol) -449.80 -276.70 -623.60 -623.40 -554.10
Cp(kJ/kmol.°C) 189.5 76.82 206.90 207.00 138.60

Table 1.6 Stream Summary Table (Continued)

Stream Number 6 7 8 9 10
Temperature (oC) 40.00 48.72 27.31 235.00 235.00
Pressure (kPa) 20000.00 1020.00 1020.00 1000.00 1000.00
Vapor Fraction 1.00 1.00 1.00 1.00 1.00
Mass Flow (kg/h) 870.00 870.00 1459.00 1459.00 12967
Mole Flow (kmol/h) 431.5476 431.5476 702.50 702.50 659.00
Component Flow rates
(kmol/h)
Maleic Anhydride 0.0000 0.0000 0.0000 0.0000 0.0000
Water 0.0000 0.0000 0.0000 0.0000 288.7680
Maleic Acid 0.0000 0.0000 0.0000 0.0000 3.5680
Hydrogen 431.5476 431.5476 701.8774 701.8774 273.7260
Succinic Acid 0.0000 0.0000 0.0000 0.0000 0.0000
Tetrahydrofuran 0.0000 0.0000 0.6102 0.6102 86.2376
gamma-
0.0000 0.0000 0.0000 0.0000 6.7430
Butyrolactone
H(kJ/mol) 0.68 0.68 -0.09 5.90 -127.10
Cp(kJ/kmol.°C) 29.18 28.52 28.58 29.11 55.94

25
Table 1.6 Stream Summary Table (Continued)

Stream Number 11 12 13 14 15
o
Temperature ( C) 40.00 40.00 40.00 40.07 84.84
Pressure (kPa) 970.00 970.00 970.00 400.00 200.00
Vapor Fraction 0.43 0.00 1.00 0.00 0.00
Mass Flow (kg/h) 12967.00 11914.10 1053.00 11914.10 10804.77
Mole Flow (kmol/h) 659.00 377.00 282.00 377.00 360.20
Component Flow rates
(kmol/h)
Maleic Anhydride 0.0000 0.0000 0.0000 0.0000 0.0000
Water 288.7680 286.9339 1.8340 286.9339 280.4746
Maleic Acid 3.5680 3.5666 0.0014 3.5666 0.0124
Hydrogen 273.7260 0.0000 273.7260 0.0000 0.0000
Succinic Acid 0.0000 0.0000 0.0000 0.0000 0.0000
Tetrahydrofuran 86.2376 79.7502 6.4874 79.7502 0.0000
gamma-Butyrolactone 6.7430 6.7422 0.0009 6.7422 79.7502
H (kJ/mol) -159.90 -277.00 -5.35 -275.70 -263.50
Cp (kJ/kmol.°C) 72.00 119.30 31.23 102.90 103.70

Table 1.6 Stream Summary Table (Continued)

Stream Number 16 17 18 19 20
Temperature (oC) 151.10 64.39 64.78 146.60 151.60
Pressure (kPa) 230.00 103.40 833.40 806.70 1030.00
Vapor Fraction 0.00 0.00 0.00 0.00 0.00
Mass Flow (kg/h) 1109.00 9047.00 9047.00 6161.00 1109.00
Mole Flow (kmol/h) 16.76 150.70 150.70 85.44 16.75
Component Flow rates
(kmol/h)
Maleic Anhydride 0.0000 0.0000 0.0000 0.0000 0.0000
Water 6.4568 33.6469 33.6469 0.0000 6.4568
Maleic Acid 3.5570 0.0000 0.0000 0.0000 3.5570
Hydrogen 0.0000 0.0000 0.0000 0.0000 0.0000
Succinic Acid 0.0000 0.0000 0.0000 0.0000 0.0000
Tetrahydrofuran 0.0000 117.0594 117.0594 85.4358 0.0000
gamma-Butyrolactone 6.7382 0.0000 0.0000 0.0000 6.7382
H (kJ/mol) -423.70 -224.70 -224.60 -191.00 -423.70
Cp (kJ/kmol.°C) 160.00 169.30 169.40 224.60 160.10

26
Table 1.6 Stream Summary Table (Continued)

Stream Number 21 22 23 24 25
o
Temperature ( C) 272.30 -18.00 -18.06 -6.57 -18.06
Pressure (kPa) 1000.00 940.00 910.00 1020.00 910.00
Vapor Fraction 1.00 0.00 1.00 1.00 0.00
Mass Flow (kg/h) 1109.00 1053.00 596.80 596.80 456.10
Mole Flow (kmol/h) 16.65 282.00 274.40 274.40 7.6820
Component Flow rates
(kmol/h)
Maleic Anhydride 0.0000 0.0000 0.0000 0.0000 0.0000
Water 6.4568 1.8340 0.0240 0.0240 1.8101
Maleic Acid 3.5570 0.0014 0.0000 0.0000 0.0014
Hydrogen 0.0000 273.7260 273.7260 273.7260 0.0000
Succinic Acid 0.0000 0.0000 0.0000 0.0000 0.0000
Tetrahydrofuran 0.0000 6.4874 0.6179 0.6179 5.8695
gamma-Butyrolactone 6.7382 0.0009 0.0000 0.0000 0.0009
H (kJ/mol) -5.35 -8.13 -1.66 -1.33 -239.10
Cp (kJ/kmol.°C) 32.23 32.09 28.62 28.66 155.60

Table 1.6 Stream Summary Table (Continued)

Stream Number 26 27 28 29
Temperature (oC) -18.06 135.00 135.00 104.1
Pressure (kPa) 200.00 792.90 792.90 117.20
Vapor Fraction 0.00 0.15 0.15 0.00
Mass Flow (kg/h) 456.10 2886.00 2886.00 5084.00
Mole Flow (kmol/h) 7.6820 65.27 65.27 282.10
Component Flow rates
(kmol/h)
Maleic Anhydride 0.0000 0.0000 0.0000 0.0000
Water 1.8101 33.6468 33.6468 282.0889
Maleic Acid 0.0014 0.0000 0.0000 0.0138
Hydrogen 0.0000 0.0002 0.0002 0.0000
Succinic Acid 0.0000 0.0000 0.0000 0.0000
Tetrahydrofuran 5.8695 31.6235 31.6235 0.000
gamma-Butyrolactone 0.0009 0.0000 0.0000 0.0009
H (kJ/mol) -238.70 -231.80 -231.80 -278.90
Cp (kJ/kmol.°C) 148.70 139.90 121.70 75.75

27
1.6.4 Process Equipment

Table 1.7 shows the details for equipment used in the production of THF.

Table 1.7 Equipment Details

Equipment Function
Maleic Acid Continuous Stirred Tank  To mix liquid Maleic Anhydride with
Reactor (R-100) water.
 The mixed Maleic Anhydride and water
steadily reacts together to yield Maleic
Acid.
 This reactor runs in continuous flow
process.
THF Packed Bed Reactor (R-101)  Formation of THF takes place in this
reactor.
 Maleic Acid and Hydrogen reacts in the
presence of Pd/Re catalyst to yield THF.
 The by product is GBL and water.
Separator (V-100 and V-101)  Separate Hydrogen from the product
stream.
Reactor Column (T-100)  Separate unreacted Maleic Acid and
GBL from product stream.
 Overhead stream contains THF and
water.
 Bottom stream contains Maleic Acid,
GBL and water.
Distillation Column (T-101)  First distillation column for pressure
swing distillation.
 Separate THF from water.
 Overhead contain THF/water mixture at
azeotrope, 93.3 wt% THF and 6.7 wt%
water.

28
Table 1.7 Equipment Details (Continued)

Equipment Function
Finishing Column (T-102)  Its function is to break THF/water
azeotrope.
 Operate at 7 bar higher than T-101.
 Uses pressure swing concept.
 Bottom product contains polymerization
grade THF.
 Overhead product contains THF and
water which is recycled back to T-101.
Pump (P-100, P-101, P-102)  Moves fluid by mechanical action.
 Pressurized the fluid.
Heater (E-100, E-101, E-104)  Heat the cold stream to the desired
temperature.
Cooler (E-102, E-103)  Cool the hot stream to the desired
temperature.
Valve (VL-100V0, VL-101, VL-102, VL-  Induce pressure drop to control the fluid
103) pressure and flow rate.
Storage Tank (V-102)  Storage of product.

29
1.6 CONCLUSION

There are three major processes that are involved in THF production. They are Reppe
process, Davy process and Furfural/Pentose process. Each of the processes has been
extensively reviewed from various literatures. The process selection in this chapter is
focused on the selection of the best process for THF production.

Among these three processes, only one process is chosen for this project. To
choose the best process, weightage scoring analysis is performed for the selection process.
The criteria for the scoring are raw material, operating condition, catalyst, product selectivity,
production capacity, economic value, safety factor and desired product quality. Davy
process scored the highest in the analysis. Therefore, after taking several considerations,
Davy process has been chosen as the process for this project production of THF.

Raw materials used in Davy process are Maleic Anhydride and Hydrogen. Maleic
Anhydride is mixed first with water to yield Maleic Acid. Maleic Acid is then mixed with
Hydrogen in the presence of Pd/Re catalyst to form THF. The THF formed using this
process is polymerization grade monomer with water wt% below than 200 ppm.

30
1.7 REFERENCES

Dreyfuss, P. (1982). Poly(tetrahydrofuran). New York: Gordon and Breach.

Godawa C, Merat N, and Gaset A, High selective production oftetrahydrofurfuryl alcohol:

Catalytic hydrogenation of furfural and furfuryl alcohol. J Chem Technol Biotechnol
48:145–159 (1990).

Elvers, B., Hawkins, S., & Schultz, G. (1991). Ulmann's encyclopedia of industrial chemistry.
Weinheim, Germany: VCH.

Hunter RL, Olsen MR, Jagannath C, Actor JK (2006). Multiple roles of cord factor in the
pathogenesis of primary, secondary and cavitary tuberculosis including the revised
description of the pathology of the secondary disease. Ann. Clin. Lab. Sci., 36: 371-
386

Matthey, J. (2015). Johnson Matthey - Davy Technologies. Davyprotech.com. Retrieved 13

December 2015, from http://davyprotech.com/what-we-do/licensed-processes-and-
core-technologies/licensed-processes/butanediol-thf-gbl/specification/

Turton, R. (1998). Analysis, synthesis, and design of chemical processes. Upper Saddle
River, N.J.: Prentice Hall PTR.

Wikipedia,. (2015). Tetrahydrofuran. Retrieved 13 December 2015, from

https://en.wikipedia.org/wiki/Tetrahydrofuran

31