Methanol Catalyst Poisons - A Literature Study (CCS)

Clean Hydrogen-rich Synthesis Gas
Contract No: SES6-CT-2004-502587

Report No: CHRISGAS March 2009_WP3_D14
Deliverable Number D14
Budgetary Assessment of Post-CHRISGAS
Transportation Fuel Installation
Part 1 - Methanol Catalyst Poisons: A Literature Study

Work Package: 3a Task: 3a.4: Costing of Gas Upgrading Equipment
Contributing & Responsible Partner: CCS
Distribution: Public
Date: March 2009
Revision history:
Rev. no. Date Change information
0

Methanol catalyst poisons

A literature study

Report
IND07002
06.25 Chrisgas
Versie 1.1

Authors: M. Rep, R.L. Cornelissen, S. Clevers
Deventer, May 2007

CCS B.V.
Energie-advies
Welle 36
7411 CC Deventer
tel. 0570-667000
fax 0570-667001
info@cocos.nl
Report No: CHRISGAS_May 2007_WP3a_
2
Contents

Summary 3
1 Introduction 4
1.1 Methanol utilisation and market value 4
1.2 Methanol production and reaction conditions 5
1.3 Industrial methanol catalysts 6
1.4 Methanol reactor types 7
2 Potential methanol catalyst poisons 8
2.1 Sulphur compounds 9
2.2 Halogen compounds 10
2.3 Nitrogen compounds 10
2.4 Phosphorus compounds 11
2.5 Metallic compounds 11
2.6 Steam 12
2.7 Lubricating oil 13
2.8 Industrial removal of poisons from syngas feed 13
2.9 Conclusions 13
3 Further recommendations 15
Glossary 16
References 17
3
Summary
The EU project Chrisgas
1
aims at the production of a clean hydrogen-rich synthesis gas
from biomass in the wood gasification plant in Vrnamo, Sweden. The gasification plant
has an hourly throughput of maximum 4 ton biomass per hour. The hydrogen-rich
synthesis gas can subsequently be used for the production of methanol, dimethyl ether,
hydrodgen, Fischer Tropsch diesel and other chemicals.
The task of CCS is to make the design for the methanol plant. The design will include the
methanol reactor and the distillation train downstream of the methanol reactor.
Methanol is produced from syngas using a state-of-the-art Cu/ZnO catalyst on an
aluminaoxide support. During the project meeting in Vrnamo of February 5
th
, 2007, the
need to investigate possible methanol catalyst poisons was discussed. Possible catalyst
poisons include sulphur compounds, chlorine containing compounds and alkali metals.
This report will describe known methanol catalyst poisons as well as how to treat the gas
upstream.

1
Chrisgas: Acronym for Clean Hydrogen-rich Synthesis Gas
4
1 Introduction
1.1 Methanol utilisation and market value
Methanol is primarily used to produce formaldehyde, methyl tertiary butyl ether (MTBE)
and acetic acid, with smaller amounts going into the manufacture of dimethyl
terephthalate (DMT), methylmethacrylate (MMA), chloromethanes, methylamines, glycol
methyl ethers, and fuels. It also has many general solvent and antifreeze uses, such as
being a component for paint strippers, car windshield washer compounds and a de-icer
for natural gas pipelines.
In 2004, around 34% of global methanol is used to produce formaldehyde, 21% for
MTBE and other fuel additives, and 9% for acetic acid. MTBE's share has been declining
following the decision to phase out its use in California and other states in the US.
However, increased use in eastern and central Europe and Asia could partly compensate.
Methanol used in the production of DMT is declining as purified terephthalic acid (PTA)
gains share in the polyester market (although partly offset by increased acetic acid
consumption in PTA manufacture).
However, a number of new applications for methanol are envisaged, especially as the
cost of production can be reduced by installing production facilities consuming low cost
natural gas in the Middle East. For example, it could be used to make ethylene and
propylene, dimethyl ether as a substitute for diesel fuel, in hydrogen production instead
of naphtha, and in power generation. The development of methanol fuel cells, for
automotive, stationary power and portable electronic equipment applications, could
provide a boost to consumption later this decade.
The European methanol contract value for the first quarter of 2007 (dated March 16,
2007), was as high as 420 /ton (550 $/ton) fob
2
. [1] However, spot prices have
declined in the 2
nd
quarter of 2007 to below 250 /ton. It is expected as contract
negotiations for the 2
nd
quarter of 2007 have begun at less than 300 /ton market prices
have had their highest point. The development of the methanol market value (contract
and spot prices) since 1998 are shown in figures 1.1 and 1.2.

Figure 1.1: Methanol contract prices in Western Europe, USA and Asia.

2
fob: free on board; It means that the seller pays for transportation of the goods to the port of shipment, plus loading
costs. The buyer pays freight, insurance, unloading costs and transportation from the port of destination to the factory.
The passing of risks occurs when the goods pass the ship's rail at the port of shipment.
5

Figure 1.2: West European, US and Asian methanol spot prices.
1.2 Methanol production and reaction conditions
Methanol, a C1-molecule, is mainly produced from synthesis gas and is the simplest of
the series of aliphatic alcohols. Methanol, or wood alcohol, is produced by the
hydrogenation of carbon oxides over a suitable catalyst, according to the following
reactions:

Typical reaction conditions are a temperature of 200 - 300 C and a pressure of 5 - 11
MPa. Because the volume of the products is less than the volume of the reactants, higher
pressures and lower temperatures favour higher syngas conversion.
Methanol synthesis, which uses H
2
-rich syngas, yields a crude methanol product with 4 %
to 20 % water by weight. If a CO-rich syngas would be used the product would contain
less water. As a result, raw methanol would be suitable for many applications at a
substantial savings in purification costs. However, methanol production reactions are
exothermically limited; both above reactions are highly exothermic.
For syngas with a high carbon monoxide content, conversion is limited by hydrogen
availability. If a higher conversion is desired than the hydrogen content of the syngas
permits, one option is to utilize the inherent shift conversion activity of the methanol
catalyst. This is done by adding steam to the reactor feed. The steam reacts with some of
the carbon monoxide to form additional hydrogen as shown below:

The hydrogen thus produced reacts with carbon monoxide to form additional methanol.
The extent of this reaction is equilibrium limited, and if syngas conversion in excess of 50
% is required, then a carbon dioxide removal unit can be used in conjunction with steam
addition.
It is well known that the presence of CO
2
has a positive effect on the methanol formation
of the copper/zinc oxide catalyzed reactions. Approximately 6 volume % CO
2
is normally
added to the syngas feed. [2] In the CHRISGAS project the CO
2
concentration in the gas
6
phase accounts to about 1 volume %. [3] CO
2
conditions and prevents damage to the
catalyst. Some studies have indicated that essentially all of the methanol is produced
from the reaction of CO
2
with hydrogen. [4] An internal water gas shift between the
resulting water and CO generates more CO
2
for methanol production. The following
reaction schemes show the proposed reaction mechanism.

1.3 Industrial methanol catalysts
In 1923, scientists at Badische Anilin & Soda-Fabrik AG (BASF), Germany, developed a
method to convert synthesis gas into methanol. This process used a zinc chromate
catalyst, and required extremely vigorous conditions, such as pressures ranging from 30
- 100 MPa, and temperatures of about 400 C. This catalyst was used in the high
pressure methanol synthesis up to the mid 1960s.
Modern methanol production has been made more efficient through use of catalysts
(commonly copper) capable of operating at lower pressures. Today, the most widely used
catalyst is a mixture of copper, zinc oxide, and aluminaoxide first used by The Imperial
Chemical Industries (ICI) in 1966. At 5 - 10 MPa and 250 C, it can catalyze the
production of methanol from carbon monoxide and hydrogen with high selectivity. The
reaction is carried out in the gas phase in a fixed bed reactor. The good catalyst life and
selectivity, larger capacity single-train convertor designs, power requirements, and
improved reliability of the low pressure technology result in lower energy consumption
and economy of scale. Current catalysts may contain, next to copper and zinc oxide on
alumina, other stabilisers and promoters, such as alkaline earth oxides. These have
several roles, including inhibition of sintering, and poison traps that prevent poisoning of
the active metal surface. In Figure 1.3 physical and chemical properties for a typical
methanol synthesis catalyst produced by Haldor Topse are shown. [5]

Figure 1.3: Physical and chemical properties for a methanol synthesis catalyst.
The active catalyst for methanol production is metallic copper. It is therefore desirable to
reduce the catalyst before use, for example by passing hydrogen gas through the reactor
in absence of the other components of the reaction system at 200 to 300 C. Preferably
the molar ratio Cu/Zn is 1 or greater than 1, e.g., to 10 and the Al content is 10 or less
7
mole %. Zinc oxide helps in the formation of high copper metal surface area, slows
agglomeration of the copper particles, traps Cu poisons and reacts with alumina to inhibit
dimethyl ether formation.
1.4 Methanol reactor types
As said before formation of methanol is exothermic. Removing the heat of reaction while
maintaining precise temperature control to achieve optimum catalyst life and reaction
rate is one of the most difficult design problems of methanol synthesis. Thus in a
conventional fixed bed reactor design, heat control and removal is of prime importance.
Several types of reactors have been developed to deal with this problem. Only a brief
summary of the reactors involved in MeOH will be given as they are subject of the report
concerning MeOH reaction/distillation and DME production.
Catalyst beds or particles can be cooled directly or indirectly. Heat removal in fixed bed
reactors can be facilitated by injection of cold gas in an adiabatic multibed quench
reactor, or by heating another medium such as water in a tubular cooled reactor. [11]
These beds may give rise to hotspots when heat removal is not sufficient resulting in
catalyst damage. A novel type of MeOH reactor that still is in its demo phase is a slurry
three phase bubble column methanol reactor (SBCR) used to process CO-rich syngas
originating from coal. In this reactor an inert mineral oil is used to remove the reaction
heat. The process (LPMEOH) is developed by Eastman Chemical Company and Air
Products and Chemicals, Inc. and is located at Eastman Chemical Companys chemicals-
from-coal complex at Kingsport, Tennessee. [6]
Schematic drawings of the different used industrial MeOH reactors are shown in Figure
1.4.

Figure 1.4: Schematic drawing of the industrially applied different methanol reactors: 1)
an adiabatic multibed quench reactor, 2) a tubular cooled reactor, and 3) a slurry three
phase bubble column reactor.
8
2 Potential methanol catalyst poisons
Biomass is often referred to as a clean feedstock, most accurately pertaining to wood,
which is low in mineral content; contains almost no sulphur or nitrogen; and is composed
primarily of carbon, hydrogen, and oxygen. However, other potential biomass feedstocks
are more problematic. Bark has more mineral, sulphur, and nitrogen, and leaves and
twigs (juvenile wood) even more so. Herbaceous biomass, such as switch grass, has
significant levels of mineral content, as much as 10 - 15 wt%, and a relatively high
nitrogen (2 - 4%) content as well as sulphur. Aquatic biomasses, such as kelp or algae,
have particularly high mineral contents, especially the marine species. Finally, waste
biomass often can contain higher levels of minerals (concentrated in the residue after
degradation of the organic portions) and be further contaminated with soil.
Biomass as it may incorporate compounds in high concentrations such as nitrogen and
metal compounds compared to fossil fuels may cause problems to downstream hydrogen
equipment. Deactivation of different upgrading catalysts is caused by poisoning,
generally from traces of chloride and sulphur compounds in the feed. Other types of
catalyst poisons include phosphorus, silicon and unsaturated hydrocarbons. Also other
types of deactivation occur such as sintering from the hydrothermal environment of the
reaction.
In this chapter possible methanol catalyst poisons and their effect on reaction kinetics
and selectivity will be discussed. These compounds may occur from the biomass feed or
the reactor equipment and are introduced with the gas stream to the methanol synthesis
reactor. Although an acid gas removal unit (AGR) will be installed that may remove most
contaminants some may still slip through. For example, the sulphur content of the feed
gas to the methanol synthesis plant after the AGR may be as high as 10 ppm. [3] In
Figure 2.1 elemental concentrations of possible contaminants in the gas phase after the
gasifier as function of feedstock are listed. [7]

Figure 2.1: Element concentrations in the biomasses and estimated concentrations in the
flue gas, if elements are released exclusively. Cursive values are below the detection
limit.
Several compounds containing the above elements have been identified as possible
methanol catalyst poisons. These will be discussed here. Poisonous effects were studied
in gas phase fixed bed and bubble slurry column (SBCR) reactors, respectively, however,
results obtained for the liquid phase process are also applicable to the gas phase fixed
bed MeOH synthesis process. [8]
9
2.1 Sulphur compounds
Sulphur compounds, such as hydrogen sulphide (H
2
S), carbon disulphide (CS
2
), carbonyl
sulphide (COS), and organo sulphur compounds (such as thiophene (C
4
H
4
S) and methyl
thiocyanate (CH
3
SCN)) have been identified as potential methanol catalyst poisons. [8]
These compounds, and particularly H
2
S, form stable compounds on the catalyst surface
and block its active sites. Initial reaction is most likely the hydrogenation of COS, CS
2
,
C
4
H
4
S, and CH
3
SCN catalyzed by the active copper metal surface. [9] H
2
S, the sulphur
containing product, will then react with metallic copper to form CuS
2
. There appears to
be evidence that the copper poisoning by sulphur containing compounds in the presence
of H
2
is reversible. The maximum allowable sulphur content of the synthesis gas fed to
the loop is 0.1 ppm v/v as H
2
S. [10,11] No reports were found describing the effects of
thiols, such as methanethiol (CH
3
SH), but based on the results for other sulphur
containing compounds, these species are likely to be potent catalyst poisons.
In Fig 2.2 the effect of carbonyl sulphide on the synthesis rate of methanol is shown.
[12] It should be noted that the graph was made for CO rich synthesis gas compared to
the synthesis gas from Vrnamo, indicating that the effect of COS on methanol catalysts
using hydrogen rich syngas may be different.

Figure 2.2: Effect of admission of carbonyl sulphide (COS) on the production rate of
methanol
As sulphur compounds have been shown to be potent copper poisons, in practice sulphur
poisoning appears to be less of a problem. The presence of zinc oxide on the methanol
synthesis catalyst namely acts as a sulphur absorber; ZnO reacts with H
2
S to form
thermodynamically stable ZnS and H
2
O providing the catalyst with improved sulphur
resistance. The small crystallite size of ZnO, coming from the method of manufacture
ensures fast absorption. [10] Most well-formulated Cu/ZnO type catalysts can retain a
high proportion of their activity in the presence of sulphur compounds. It was found that
Cu/ZnO/Al
2
O
3
methanol synthesis catalysts retain a high proportion of their activity even
when they have accumulated quite large amounts of sulphur. [10] With an average of
2% sulphur, the methanol synthesis activity of a Cu/ZnO/Al
2
O
3
catalyst was
approximately 80% of the un-poisoned activity, and with an average of 12% sulphur
activity was approximately 25% of the un-poisoned activity. In contrast, a Cu/Al
2
O
3

catalyst was completely deactivated with only 0.2% sulphur in the catalyst, showing one
of the major beneficial effects of having ZnO in Cu-based catalysts. In Figure 2.3 a
photograph of a ZnO catalyst particle reacted and unreacted with H
2
S is shown.
Severity of catalyst deactivation in the presence of sulphur poisons decreases in the
following order [8]:
C
4
H
4
S > CH
3
SCN > CS
2
> COS
10

Figure 2.3: Photograph of a zinc oxide layer. Clearly on the left side the zinc sulphide
layer formed by irreversible adsorption of H
2
S can be observed
3
.
2.2 Halogen compounds
Chlorine in any form (free or combined) is a virulent poison and should be excluded
completely from the process gas side of any equipment. It is essential that chlorinated
compounds are not introduced into the synthesis gas production section or synthesis loop
as solvents or degreasing agents during the plant construction, pre-commissioning or
maintenance periods. Hydrogen chloride (HCl) reacts with the active copper producing
low melting copper chloride (CuCl) that quickly sinters, thus reducing the copper surface
area and killing the catalyst completely. [10] Even traces of chloride markedly
accelerated sintering. The presence of chlorine caused an immediate decrease in catalytic
activity which continued even after the HCl source has been removed.
The presence of HCl will result also in the formation of zinc chloride while releasing
water. The formation of zinc chloride will, however, effect the sulphur absorption capacity
of the ZnO catalyst and thus the sulphur tolerance of the copper catalyst. [6] Another
major problem is the high mobility of the zinc chloride under reaction conditions, which
also influences the thermal stability of the catalyst. [10] To avoid the formation of zinc
chloride, HCl guard beds, such as potassium carbonate on an activated alumina carrier,
should be installed upstream the zinc oxide sulphur absorption step. [13] From
experimental work it is clear that ZnO can give no protection to Cu catalysts against HCl
poisoning. [10] Based on experimental evidence the limits on HCl content in the syngas
feed to avoid catalyst poisoning are of the order of 1 ppb. [10]
Other organic halogen compounds such as methyl chloride and methyl fluoride also affect
the rate of methanol formation. Concentrations of halogens as low as 2 ppm led to
increased deactivation. [8] However, methyl chloride was a much more active poison
compared to methyl fluoride. Initial reaction is most likely the hydrogenation of organic
halogen compounds catalyzed by the active copper metal surface, resulting in copper
chloride or copper fluoride. CuCl or CuF can be reduced to metallic copper and HCl,
indicating that halogen poisoning is reversible. To remove these halogen compounds they
need to be hydrogenated upstream of the methanol synthesis reactor.
Severity of catalyst deactivation in the presence of halogen poisons decreases in the
following order [8]:
CH
3
Cl > CH
3
F
2.3 Nitrogen compounds
Nitrogen compounds are common catalyst poisons. However, nitrogen containing
contaminants hydrogen cyanide (HCN), acetonitrile (CH
3
CN), and methylamine (CH
3
NH
2
)
had no effect on catalyst activity. Amines and nitriles have very low affinity for active
copper species. HCN is expected to react with ZnO forming Zn(CN)
2
species, however
this was not observed during MeOH synthesis. The surprising inactivity of HCN is likely

3
Courtesy of Engelhard Corporation, USA.
11
attributable to its hydrogenation under methanol synthesis conditions to methyl amine,
which was shown to have little affinity for copper. [8]
2.4 Phosphorus compounds
Phosphorus compounds, such as (substituted) phosphines (PH
3
, PR
3
) may function as
copper poisons. Phosphines can be formed by hydrogenation of phosphorous during
gasification. Poisoning by phosphine likely occurs by a reaction analogous to that
proposed for arsine. Concentrations of phosphine as low as 2 ppm led to increased
deactivation. Analysis of spent catalyst showed a very low BET surface area.
2.5 Metallic compounds
The catalyst is poisoned by metals (heavy metals or alkali metals) and arsenic
compounds.
Precautions should be taken to minimise iron carbonyl (Fe(CO)
5
) or nickel carbonyl
(Ni(CO)
4
) formation by thorough descaling of the equipment and pipework in the
optimum temperature region for carbonyl formation, i.e. in all hot parts of the loop. Iron
carbonyl can form when syngas is in contact with carbon steel (rust) while Ni(CO)
4

results from contact with 304 and 316 stainless steel. An optimum temperature for metal
carbonyl formation is about 200 C. Both carbonyl compounds are generally found in
syngas, particularly those rich in CO.
Iron and nickel carbonyls will decompose on the catalyst, as they are thermodynamically
unstable at methanol synthesis reaction temperatures. This will deposit a thin film of
highly reactive iron or nickel onto the surface of the catalyst. Apart from acting as a
catalyst poison by restricting access to the active copper surface resulting in a dramatic
loss of activity, this highly active species will increase the rate of certain by-product
reactions (Fischer Tropsch) and will catalyse the highly exothermic methanation reaction.
If this is believed to have occurred, even stricter limits should be imposed on the
maximum operating temperature of the catalyst in order to prevent excessive
methanation and hence excessive temperature rise over the catalyst bed. Methanation
over iron and nickel occurs at temperatures of 250 C. Fig 2.4 shows the effect of
transition metal carbonyls on the synthesis rate of methanol. [12] Note that although the
graphs were made for CO rich synthesis gas compared to the synthesis gas from
Vrnamo giving rise to higher concentrations of gaseous carbonyl compounds the effect
is unambiguous. After the addition of iron carbonyl was begun, the rate of catalyst
deactivation increased by about 50%. In the case of nickel carbonyl addition to the feed
a substantial increase in the rate of catalyst deactivation, roughly a factor of four,
occurred.

Figure 2.4: Effect of admission of iron (a) and nickel (b) carbonyls on the production rate
of methanol
(a)
(b)
12
Arsenic-containing species, such as arsine (see Fig. 2.5), have been found in syngas feed
to MeOH synthesis plants originating from coal. They were not mentioned in the study
performed by Porbatzki and Mller. [7] However, there are indications that biomass also
contain arsenic compounds as natural constituents and often at remarkably high
concentrations (> 100 mg As per kg wet mass). [14]

Figure 2.5: Molecular structure of arsine
Catalytic testing in the presence of arsine showed that arsine was a powerful methanol
synthesis catalyst poison. [15] Arsine, at levels as low as 150 ppbv, resulted in a rapid
deactivation of the catalyst. Removal of arsine resulted in a deactivation rate consistent
with a clean synthesis gas feed; that is, arsine poisoning stopped when it was removed
from the feed. Measurements of arsenic-containing spent catalyst indicated the presence
of zero-valent arsenic in an intermetallic surface phase that is structurally related to
Domeykite (Cu
3
As). This indicates that arsine absorbed and dissociated on the copper
surface to form gaseous H
2
and Cu
3
As. Arsine thus reacts irreversibly with the catalyst
under the methanol synthesis conditions.
In Figure 2.6 the deactivation rate of the methanol synthesis catalyst as function of the
arsine concentration in the syngas feed is shown.

Figure 2.6: Deactivation rate as function of the concentration of AsH
3
in the syngas feed.
Severity of catalyst deactivation in the presence of metallic poisons decreases in the
following order:
Ni(CO)
4
> Fe(CO)
5
> AsH
3

Poisoning by alkali metals should be considered as alkaline impurities can result in the
production of higher alcohols, and cause some decrease in activity, however, no
literature data has been found. Impurities of alkali may originate from the biomass feed,
catalyst or from carry over of solids from the boiler into the process steam system.
2.6 Steam
Steaming of the catalyst accelerates growth of the copper crystals and deactivates the
catalyst especially in the presence of chlorine containing compounds. Also it may cause
13
particle breakage that could lead to high-pressure drop and non-homogeneous
distribution of flow through large catalyst beds and impaired performance. Therefore, the
presence of steam should be avoided.
2.7 Lubricating oil
Lubricating oil may originate from used compressors, and other moving parts within the
reactor unit. Oil in quantities greater than would be passed by currently designed glass
wool filters is considered to have a deactivating effect on the catalyst, as it may block
some of the smaller pores. [11] This may also result from in-situ production of paraffins
by transition metal deposits (Fischer Tropsch) or acidic impurities.
Carbon deposition (coking) on commercial copper catalysts, is uncommon, as they are
considered not to be acidic and as they operate under mild conditions. [10]
2.8 Industrial removal of poisons from syngas feed
Test results for the LPMEOH
TM
process has indicated that the poisons identified in syngas
can be removed from the syngas feed stream. These materials are documented in Ref.
[16]. The results of adsorbent screening have led to a conceptual low temperature design
for poison removal by adsorption. The first adsorbent bed would contain spent methanol
catalyst to adsorb H
2
S and HCl in a throw-away system. The next bed would contain H-Y
zeolite for Fe(CO)
5
removal, followed by active carbon for Ni(CO)
4
removal, and finally
copper oxide/chromium oxide loaded carbon for COS removal. The sections containing
zeolite, and active carbon absorbents are thermally regenerable at 260 C. All adsorbent
materials investigated are commercially available and the process cycle is either
conventional temperature swing adsorption (TSA) or throw-away.
In the Vrnamo plant which forms the heart of the CHRISGAS project prior to the water
gas shift (WGS) reactor most contaminants may already have been removed, although
the proposed sour gas shift catalyst is stable in sulphur containing syngas. Downstream
of the WGS reactor an acid gas removal unit is placed for the removal of CO
2
. This unit
based on a water-wash design may also be effective for the removal of acidic sulphur,
halogen, and nitrogen compounds and alkali compounds. Only precaution needs to be
taken into account concerning the formation of metal carbonyls.
2.9 Conclusions
Possible methanol catalyst poisons present in the syngas feed to the methanol synthesis
reactor include sulphur, halogen, phosphorous containing compounds from biomass or
iron and nickel carbonyls form reactor equipment. Poisoning by these compounds result
in site blocking or sintering, which yields decreased activity or change in selectivity.
Based on the results of several studies, the following ranking of methanol synthesis
catalyst poison strength could be obtained [9]:
Nickel carbonyl (Ni(CO)
4
) > iron carbonyl (Fe(CO)
5
) > thiophene (C
4
H
4
S) arsine (AsH
3
)
> methyl chloride (CH
3
Cl) > methyl thiocyanate (CH
3
SCN) > carbon disulfide (CS
2
) >
carbonyl sulfide (COS) > phosphine (PH
3
) > methyl fluoride (CH
3
F).
Catalyst guard beds need to be installed for removal of these compounds. Several
maximum exposure levels of poisoning compounds to methanol catalyst synthesis
catalysts are listed in Table 2.1 together with options for poison removal.
14
Table 2.1: Apparent maximum poison concentrations for methanol synthesis catalyst and
removal technology
Poison Apparent maximum allowable
concentration
Technology
Sulphur as H
2
S 0.1 ppm ZnO guard bed;
spent methanol catalyst
Chlorine as HCl 1 ppb base promoted alumina;
spent methanol catalyst
Phosphorous as PH
3
< 2 ppm copper impregnated carbon
Metal carbonyls
Fe(CO)
5

Ni(CO)
4

AsH
3

< 1 ppm
< 1 ppm
150 ppb

H-Y zeolite
active carbon
copper impregnated carbon

15
3 Further recommendations
In Chapter 2 several possible catalyst poisons have been identified. However, these
poisons may originate from the feed, such as natural gas or coal. Therefore it may be
possible that the list in Chapter 2 is not complete.
It is therefore our recommendation to visit Sekundrrohstoff-Verwertungszentrum
Schwarze Pumpe in Germany where they produce methanol from syngas produced from
biological waste mixed with coal in different types of gasifiers [17].
Some items of discussion may be:
1) type of catalyst, reactor type and conditions;
2) catalyst poisons affiliated to biomass not present in coal and their respective
concentrations, and;
3) installed gas treatment units before methanol synthesis reactor.

16
Glossary
Abbreviation
AGR acid gas removal unit
CHRISGAS Clean Hydrogen-rich Synthesis Gas
CO carbon monoxide
CO
2
carbon dioxide
Fob free on board
H
2
hydrogen
MeOH methanol
SBCR slurry bubble column reactor
Syngas synthesis gas: mixture of hydrogen and carbon monoxide
WGS water gas shift

17
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