(

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every
C01B 1 7/04 (2006.01) B01J 20/06 (2006.01) kind of national protection av ailable) . AE, AG, AL, AM,
B 11) 53/86 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ,
CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO,
(21) International Application Number:
DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN,
PCT/EP20 19/07923 3
HR, HU, ID, IL, IN, IR, IS, JO, JP, KE, KG, KH, KN, KP,
(22) International Filing Date: KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME,
25 October 2019 (25. 10.2019) MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,
OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA,
(25) Filing Language: English
SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
(26) Publication Language: English TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.

(30) Priority Data:
PA 2018 00795 31 October 2018 (3 1 . 10.2018)
PA 2019 00654 28 May 2019 (28.05.2019)
(71) Applicant: HALDOR TOPS0E A/S [DK/DK]; Haldor
Topsoes Alle 1, 2800 Kgs. Lyngby (DK).
(72) Inventors: THELLEFSEN, Morten; Egholmen 12,
DK-3400 Hillerod (DK). BRORHOLT, Lars Piilmann;
Tollerupvej 21, DK-3370 Melby (DK). S0RENSEN, Per
Aggerholm; Gammelmosevej 179B, DK-2800 Kgs. Lyng¬
by (DK). LYKKE, Mads; Havrevej 30, DK-2700 Br nsh j
(DK).
(84) Designated States (unless otherwise indicated, for every
DK kind of regional protection available) . ARIPO (BW, GH,
DK GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ,
UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
TR), OAPI (BF, BJ, CF, CG, Cl, CM, GA, GN, GQ, GW,
KM, ML, MR, NE, SN, TD, TG).

(54) Title: METHOD FOR PRODUCTION OF SULFUR

(57) Abstract: The present invention relates to process plant comprising a Claus reaction furnace, a Claus waste heat boiler, a SO3
destruction section and a Claus conversion section, wherein the Claus reaction furnace has an inlet and an outlet, the Claus waste heat
boiler has a gas inlet, a gas outlet and optional an elemental sulfur outlet, the SO3 destruction section has a gas inlet and a gas outlet
and the Claus conversion section has a gas inlet, a gas outlet and an elemental sulfur outlet, and wherein the inlet of the Claus reaction
furnace is configured for receiving a feedstock gas, sulfuric acid, fuel, an oxidant and an optional sulfuric acid atomization media, and
the outlet of the Claus reaction furnace is configured for being in fluid communication with the inlet of the Claus waste heat boiler,
wherein the outlet of the Claus waste heat boiler is configured for being in fluid communication with the inlet of the SO3 destruction
section, wherein the outlet of the SO3 destruction section is in fluid communication with the inlet of the Claus conversion section. The
process has the associated benefit of such a process avoiding undesired poisoning (sulfation) of Claus catalyst and contamination of
elemental sulfur product with sulfuric acid in the Claus conversion section.

[Continued on next page]

| || ||||| ||||| ||||| |||| 1 1| ||| ||||| ||||| ||||| ||||| mil III III! III! llll
Title: Method for production of sulfur

The present invention is related to a process for conversion of I-I2S to elemental sulfur
in a Claus process plant in which H2SO4 is added to the thermal stage of the Claus pro-

cess plant.

H2S is a common side product in many processes, including hydrodesulfurization of re-

finery streams, production of viscose and natural gas sweetening. It is desirable to con-
vert H2S prior to emission to the atmosphere as H2S is highly toxic, odorous and an en-
vironmental challenge.

Refinery processes, besides producing the well-known high concentration H2S gas,
may often also produce a so-called sour water stripper gas, which comprises H2S, H2O
and N H 3 in around equal molar amounts.

Especially in refineries, the chosen process for H2S abatement has been the Claus pro-
cess, which has been known and optimized for more the 8 decades. The Claus pro-
cess proceeds by sub-stoichiometric combustion of H2S producing SO2 in a Claus re-
action furnace, providing a Claus converter feed gas. The subsequent Claus process
will convert the remaining H2S and the formed SO2 to form elemental sulfur, which may
be condensed and withdrawn.

It has now been identified that addition of sulfuric acid to the Claus reaction furnace
provides opportunities for optimization of the Claus process plant size and operational
cost. H2SO4 is a concentrated source of O 2 and a temperature moderator. Both proper-
ties are valuable for capacity boosting of the Claus process. It has also been identified
that this addition of H2SO4 may damage the catalyst of the Claus process by sulfation
and thus require an SO3 guard prior to the catalytic Claus process.

In WO 2012/152919 A 1 , a sulfuric acid process for treatment of Claus tail gas is pre-

sented in which the conversion of H2S to H2SO4 in a Claus tail gas is described. The
steps in the process are:

1. Sub-stoichiometric oxidation in Claus reaction furnace

2 . Claus conversion
3 . Oxidation of reduced sulfur species (H2S) in the Claus tail gas in oxygen rich at-
mosphere at 400-700 °C
4 . Catalytic oxidation of SO2 to S O 3
5 . Condensation of H2SO4
It is recognized that the H2SO4 product is not always desirable and it is suggested to

recycle the sulfuric acid to the upstream Claus reaction furnace or the H2S oxidation
step as described above. However, the recycling of sulfuric acid is merely thought as
an abatement of sulfuric acid, and the consequences of recycling the H2SO4 on the sul-
furic acid or Claus process have not been evaluated, i.e. it is not recognized that H2SO4
recirculation requires a reduction in the amount of O 2 directed to the Claus reaction fur-
nace, nor are the beneficial effects on the Claus and sulfuric acid process realized.
Also the effect on the chemistry in the Claus plant has not been considered. Finally, the
document contains no consideration of incomplete conversion of H2SO4 to SO2 - there-
fore absence of S O 3 in the Claus process is a core assumption in this document, and
no considerations are given to requirements for removal of S O 3 .

The sulfuric acid does not have to be recycled from a downstream sulfuric acid plant
acting as a Claus tail gas treatment plant, but can come from other sources. The bene-
fit of adding H2SO4 to the Claus process plant can justify purchase of H2SO4, as the
H2SO4 both acts as an efficient O 2 carrier and temperature moderator as described in
patent application PCT/EP201 7/080721 . The addition of H2SO4 can boost the capacity
of the Claus process plant by up to 50% without affecting the process gas flow in the
Claus process plant.

In Danish patent application PA 2018 00057 different means of adding the liquid H2SO4

stream to the thermal stage of the Claus process plant, also known as the Claus reac-
tion furnace, is described. It is important to ensure that the injection does not interfere
significantly with the flame in the reaction furnace, while still being close to the hot
flame for fast evaporation and subsequent mixing with the gas phase to carry out the
desired Claus reaction.

The prior art relating to feeding H2SO4 to the thermal stage of the Claus process plant
has assumed full evaporation of sulfuric acid and quantitative conversion to SO2. How-
ever, the present disclosure is related to the realization that this conversion of H2SO4 to
SO2 may not be complete.

In a broad aspect the present invention relates to a process for production of a sub-

stantially S O 3 free Claus converter feed gas from a feedstock gas comprising 30 vol%,
40 vol% or 50% to 99 vol% or 100 vol% H2S and a stream of sulfuric acid involving the
steps of
a. providing a Claus reaction furnace feed stream comprising said feedstock gas,
an amount of sulfuric acid, an amount of molecular oxygen and optionally an amount of
fuel, wherein the amount of molecular oxygen is substoichiometric,

b. directing said Claus reaction furnace feed stream to a Claus reaction furnace
operating at elevated temperature, such as above 900°C, providing a Claus reaction
furnace off gas

c. cooling said Claus reaction furnace off gas and optionally withdrawing ele-
mental sulfur from the gas

d. directing said cooled Claus reaction furnace off gas to contact an S O 3 guard
material, absorbing and/or converting S O 3 , providing a substantially S O 3 free Claus
converter feed gas

e. directing said substantially S O 3 free Claus converter feed gas to contact a ma-
terial catalytically active in the Claus reaction

f. withdrawing elemental sulfur, optionally by cooling the effluent from said mate-
rial catalytically active in the Claus reaction,

characterized in said S O 3 guard material being different from said material catalytically
active in the Claus reaction, wherein said S O 3 guard material active in S O 3 removal en-
sures a long operation of the catalyst active in the Claus reaction, if droplets of sulfuric
acid are not fully evaporated and reduced in the gas phase, such that long operation of
the Claus process plant can be maintained, even when said material catalytically active
in the Claus reaction has no activity or only temporary activity in S O 3 conversion or ab-

sorption.

In a further embodiment, the S O 3 guard is an S O 3 absorbent, in which the content of

S O 3 is increased over time, such as alumina or titania, with the associated benefit of

such an absorbent being inexpensive, and with the further benefit of alumina and tita-
nia having a moderate catalytic effect, allowing for some conversion of absorbed S O 3 .

In a further embodiment, wherein the S O 3 guard material is a material catalytically ac-

tive in reducing S O 3 by reaction with H 2S , providing a substantially S O 3 free Claus con-

verter feed gas, with the associated benefit of the lifetime of the S O 3 guard material not
being limited by an absorption capability.
In a further embodiment the SO 3 guard material is arranged downstream the Claus re-

action furnace and upstream the Claus converter, with the associated benefit of the
SO 3 guard material being remote and thus independent from the flame in the Claus re-
action furnace.

In a further embodiment the SO3 guard material is arranged as top layer on material

catalytically active in the Claus reaction, with the associated benefit of avoiding the cost
of a separate reactor for the SO 3 guard.

In a further embodiment the material catalytically active in the reduction of SO 3 corn-

prises one or more elements taken from the group consisting of V, Mn, Fe, Co, Cu, Zn,
Ni, Mo, W, Sb, T i and Bi and a support comprising one or more elements taken from
the group consisting of Al, Ti, Si, Zr and Mg, with the associated benefit of such materi-
als being active in the conversion of SO 3 to SO 2 or sulfur.

In a further embodiment the support comprises diatomaceous earth and/or cordierite

with the associated benefit of such materials being stable and having a high surface
area.

In a further embodiment the material active in the reduction of SO 3 is in shape of pellets

or a monolith, with the associated benefit of pellets being cost effective to produce,
whereas monoliths benefit from having a low pressure drop.

In a further embodiment the Claus reaction furnace is operated at a temperature of be-

tween 900°C and 1500°C with the associated benefit of this temperature range being
appropriate for decomposition of H2SO4 to H2O and SO 3, for further decomposition of
SO 3 to SO 2 , for partial oxidation of H2S and for decomposition of impurities.

In a further embodiment the material catalytically active in reducing SO 3 is operated at

a temperature of between 130°C and 1500°C with the associated benefit of the temper-
ature being appropriately inside the interval of catalytic Claus reaction and non-catalytic
Claus reaction furnace temperatures.

In a further embodiment the material catalytically active in reducing SO 3 is operated at

a temperature of between 250°C and 500°C, with the associated benefit of operating in
a temperature range where conversion from SO 3 to SO 2 and/or sulfur is rapid without
requiring high resistance materials.

In a further embodiment the material catalytically active in reducing SO 3 is operated at

a temperature of between 300°C and 400°C, with the associated benefit of operating in
a temperature range where conversion from SO3 to SO 2 or sulfur is rapid without re-
quiring exotic materials.

In a further embodiment the stream of sulfuric acid is produced in a wet type sulfuric

acid plant treating the tail gas from the Claus plant with the associated benefit of such a
process being thermally efficient and able to reduce emission of sulfurous compounds
to a very high extent.

The liquid phase term sulfuric acid means a mixture of H2SO4 and H2O as H2SO4 is hy-
groscopic and will absorb water from the gas phase. In principle any concentration of
H2SO4 can be injected into the Claus reaction furnace, but high concentrations are de-
sired as that will reduce the energy required for evaporation and minimize the dilution
of Claus reaction furnace off gas with the associated water. For practical purposes,
only sulfuric acid with >90 %w/w H2SO4 is considered most relevant.

The gas phase terms H2SO4 (sulfuric acid) and S O 3 (sulfuric anhydride) are often just
called “SO3” as the hydration reaction of SO3 (SO3 + H2O → H2SO4) is considered very
fast and safely can be considered to be in chemical equilibrium. The distribution be-
tween S O 3 and H2SO4 depends on the temperature, pressure and H2O concentration in
the gas, S O 3 is favored at high temperatures and low H2O concentrations and H2SO4 is
favored at low temperatures and high H2O concentration. Above 400 °C, very little
H2SO4 exist and below 200 °C, very little S O 3 exist and in the range 200-400 °C both
molecules will be present in varying amounts (in case of a wet gas).

The following H2SO4 related chemical reactions will take place in the reaction furnace:

H2SO4 (liquid) H2S0 4 (gas) (1)

H2SO4 (gas) SO3 (gas) + H2O (gas) (2)

SO3 (gas) SO2 (gas) + 0.5 O 2 (3)

SO 3 (gas) + H2S (gas) SO 2 (gas) + S (gas) + H2O (gas) (4)

H2S(gas) + 1.5 O 2 SO2 (gas) + H2O (gas) (5)

SO 2 (gas) + 2 H2S (gas) 3 S (gas) + 2 H2O (gas) (6)

“S” represents elemental sulfur in any form from S2 to S s

Reactions (5) and (6) are the overall reactions for the Claus process in which the H2S
in the feed gas is combusted with O 2 deficiency to form a combustion gas with a
H2S/SO2 ratio around 2 , which is the optimal ratio for highest conversion into elemental
S.

As H2SO 4 is introduced it is seen from reaction (2) + (3) that the sulfuric acid is decom-
posed to SO 2 and O 2, ultimately reducing the O 2 requirement by 2 moles for each mole
H2SO 4 added. With air as the O 2 source, the 2 moles of O 2 are associated with 8 moles
of N2 and thus the addition of H2SO 4 significantly reduces the amount of inert gas in the
process gas.

Reaction (1) describes the evaporation of the liquid sulfuric acid after injection into the
reaction furnace. Typically, the sulfuric acid stream is atomized into a “fog” consisting
of small droplets, the droplet size distribution is determined by the method of atomiza-
tion. The droplets evaporate from the outer droplet surface and thus the initial droplet
size is essential for the time required for complete evaporation. The time for complete
evaporation depends on the 3 rd power of the droplet diameter, i.e. a doubling of the
droplet diameter increases the evaporation time by a factor of 8 . Process gas tempera-
ture and gas/droplet mixing also have a significant impact on the evaporation time of
the droplets.

To achieve the smallest droplets, two phase atomization is required in which an atomi-
zation media, which typically is compressed air, N 2 or steam, is used to “cut” the liquid
stream into fine droplets.

Reaction (2) is a very fast gas phase reaction and chemical equilibrium between SO 3
and H2SO 4 can be safely assumed.

Reaction (3) and (4) describes the overall reactions for destruction of the SO 3 into ei-
ther SO 2 and O 2 , which can then react with H2S via reaction (5) and (6) or react directly
with H2S to form SO 2 and S , where the SO 2 can react with H2S via reaction (6).

Reaction (3) is highly temperature dependent and only takes place at higher tempera-
ture, i.e. > 800 °C, unless a catalyst is present.

Reaction (4) takes place at lower temperatures too, but the reaction rate at tempera-
tures below 400 °C may be too low to be relevant for industrial applications.

At the Claus reaction furnace temperature, reactions (2) to (6) are very fast and will typ-
ically proceed to chemical equilibrium within less than 0.5 seconds. The residence time
in a reaction furnace is typically less than 1-2 seconds.
According to chemical equilibrium calculations, neither H 2SO 4 , S O 3 nor O 2 will be pre-
sent in the process gas at Claus reaction furnace gas conditions.

The stoichiometric balance between H 2S and O 2 in the absence of H 2S O 4 is 2:1 . How-

ever, in the presence of H 2SO 4 less O 2 is required. A substoichiometric amount of mo-
lecular oxygen is therefore defined as an molar amount being less than half of the mo-
lar amount of H 2S .

The Claus reaction furnace is preferably operated at a temperature between 900 and
1500°C.

For relatively large droplets, reaction (1) will be the limiting step for the reactions to pro-
ceed to equilibrium and the available 1-2 seconds of residence time can become too
short for the completion of the reactions. Such situations can arise if e.g. the nozzle for
the sulfuric acid atomization has become worn and/or the flow or pressure of the atomi-
zation media is out of the normal range. The consequence of this is that H 2S O 4 / S O 3
leaves the Claus reaction furnace not fully converted and enters the heat exchanger
(waste heat boiler) that cools the Claus reaction furnace gas to around 300-400 °C. At
this temperature reaction (1) and (2) are still active, whereas reaction rates for (3) to (6)
are too low to be of any practical significance.

In a commonly used Claus process layout, the 300-400 °C Claus reaction furnace off

gas is sent to a catalytic Claus reactor in which a catalyst active in reaction (6) is in-
stalled. This catalyst is well known in the industry and is most often used as pellets with
the active material being T1O2 or AI2O3. Also well known is that this catalyst is sensitive
to “sulfation”, i.e. the active sites of the catalyst become “poisoned” with sulfate and
thus the catalyst loses catalytic activity with the consequence of less product being
formed and increased emissions of H2S and SO2. The sulfate can be formed by reac-
tion between SO2 and O2, forming SO3 on the catalyst surface, or SO3 present in the
process gas can directly attach to the catalyst surface.

In another Claus process layout, the 300-400 °C Claus reaction furnace off gas is di-

rected to a sulfur condenser, in which the process gas is cooled to 130-160 °C to con-
dense the elemental sulfur and withdraw the product. The process gas is then reheated
and directed to a catalytic Claus reactor as described above. If there is SO3 present in
the Claus reaction furnace off gas, there is a risk of condensing sulfuric acid in the ele-
mental sulfur product, producing an off-spec product and there is an increased risk of
corrosion of the sulfur handling equipment. The off gas from the sulfur condenser will
also contain a fraction of the S O 3 (as H 2S O 4 ) present in the Claus reaction furnace off
gas and this S O 3 will poison the downstream Claus catalyst.

A s described, it is of great importance that the Claus reaction furnace off gas does not
contain substantial amounts of S O 3 as it can have a detrimental effect on the down-
stream catalyst, equipment and operation of the Claus process plant.

To ensure a safe and long operation of the Claus process plant, a new catalyst, active
in the reaction of S O 3 with H 2S to form a mixture of S O 2 and S , has been developed.

The catalyst is also able to suppress the reaction with SO 3 forming O 2 (reaction 3) as a
O 2 slip is just as problematic as a SO 3 slip. The catalyst is preferably to be installed be-
tween the outlet of the waste heat boiler connected to the Claus reaction furnace and
the inlet to equipment and/or catalysts that can be damaged by the presence of S O 3 .
This new catalyst can either be installed in a separate reactor as would be necessary in
the Claus process layout in which the cooled Claus reaction furnace off gas is sent to a
sulfur condenser before the catalytic Claus reactor or as a top layer in the existing
Claus reactor which is possible in the layout where the process gas goes directly to the
catalytic Claus reactor.

In another embodiment, the catalyst is installed at the outlet of the Claus reaction fur-

nace, taking advantage of the high temperature and high reaction rates.

The catalyst can be of any shape and size, considered optimal for the Claus process
plant layout. If to be installed as a top layer in the Claus reactor, a pellet shaped cata-
lyst would be most desirable as the Claus catalyst typically is pellet shaped.

In case the material catalytically active in reducing S O 3 (and H 2S O 4 ) by reaction with

H2S is to be installed in a separate vessel, either pellet shape catalyst or monolithic cat-

alyst can be installed, depending on the available pressure drop on the process gas
side, space limitations for the reactor and which solution is the most cost efficient.

The material catalytically active in reducing SO3 (and H2SO4) by reaction with H2S corn-
prises one or more compounds of V , Mn, Fe, Co, Cu, Zn, Ni, Mo, W , Sb, T i and Bi sup-
ported on one or more compounds of Al, Ti, Si, Zr, Mg, and cordierite, often with the
support comprising diatomaceous earth. Although AI2O3 and T1O2 alone are prone to
sulfate poisoning, the compounds can be used for support for the compounds active in
the conversion of SO3 into SO2 and S , which are harmless for the downstream Claus
catalysts. It is further considered likely that A I2O 3 and T1O 2 may act as guards by ab-
sorption of SO 3 by sulfation, and thus such materials without active metals may func-
tion as guard, but require occasional replacement or re-activation.

The material catalytically active in reducing SO 3 (and H2SO 4 ) by reaction with H2S is
operated at a temperature of between 130 and 1500°C, such as between 250 and
500°C or between 300 and 400°C.

Figures:

Figure 1 shows a Claus reaction furnace with 1st Claus reactor upstream 1st sulfur con-
denser

Figure 2 shows a Claus reaction furnace with 1st sulfur condenser upstream 1st Claus
reactor

In Figure 1, the feeds to the Claus reaction furnace (Claus thermal stage) are one or

more acid gases comprising H2S (2), an optional fuel gas (4), an oxygen source (6) be-
ing typically air with 2 1 vol% O 2 or enriched air with 21-100 vol% O 2 and a sulfuric acid
stream (8). The sulfuric acid stream can optionally be concentrated sulfuric acid pro-
duced in a sulfuric acid plant installed as a tail gas treatment plant for the Claus pro-
cess plant. The sulfuric acid atomization method that produces the smallest droplets is
a two-phase atomization in which an atomization media (10) is used to “cut” the sulfuric
acid liquid into droplets. The atomization media is most often pressurized air or steam,
but other media are also possible, such as fuel gas, enriched air or process gas.

In the Claus reaction furnace chamber (12) part of the H2S is oxidized to SO2 which

then combines with H2S to form elemental sulfur. Sulfuric acid is evaporated and reacts
with H2S to from SO2 and elemental sulfur. The temperature in the reaction furnace is
typically above 900 °C and the average residence time is typically 1-2 seconds. The off
gas from the reaction chamber (14) is led through heat exchanger (16), where the pro-
cess gas is cooled to 300-400 °C. The heat exchanger is typically a waste heat boiler,
producing high pressure steam. If elemental sulfur is condensed in the heat exchanger,
it is drained via the liquid outlet (18).

The cooled Claus reaction furnace off gas (20) is then passed through one or more
layer(s) of catalyst (22) in which any SO 3 in the Claus reaction furnace off gas is effi
ciently converted to SO 2 and S by reaction with H2S , producing a substantial SO 3 free
feed gas (24) to be directed to the Claus catalyst layer in the Claus reactor (26). It can
be possible to combine (22) and (26) such that the SO3 destruction catalyst in (22) can
be a top layer in the Claus reactor (26).

In the Claus reactor (26) more elemental sulfur is formed by reaction between H2S and

SO2 and the Claus reactor off gas (28) is passed to a first sulfur condenser (30) in
which the process gas is cooled and a fraction of the elemental sulfur condensed and
withdrawn as a liquid via outlet 32. The off gas (34) is typically reheated and passed
through one or more Claus reactor - sulfur condenser - reheater passes to ensure suf-
ficiently high conversion of H2S into elemental sulfur.

In Figure 2 the Claus reaction furnace (12) and waste heat boiler (16) are similar to the

layout and operation as described for figure 1. The difference in the layout is that the
cooled Claus reaction furnace off gas (20) is passed directly to the first sulfur conden-
ser (30) to condense and withdraw elemental sulfur product via line 32 before the con-
denser off gas (34) is reheated and passed to 1st Claus reactor. In this layout, due to
withdrawal of product, the Claus reaction equilibrium is favored in the 1st Claus reactor
and thus a higher overall conversion out of 1st Claus reactor can be achieved. For such
a layout it is necessary to install the material catalytically active in reducing SO 3 (and
H2SO4 ) by reaction with H2S in a separate vessel (22), such that a substantially SO 3
free process gas (24) enters the first sulfur condenser (30), thereby avoiding possible
contamination of sulfur product with sulfuric acid and avoiding passing uncaptured sul-
furic acid to the downstream first Claus reactor.

Example 1:

In a laboratory scale setup, the non-catalytic reaction between H2S and SO 3 has been

investigated in a reaction chamber, which consist of a 40 cm long 013 mm glass tube

installed in a temperature controlled oven.

The H2S was supplied from a gas cylinder and diluted with N 2 before added to reaction
chamber. A 2 nd N 2 stream was saturated with water to have H2O present in the process
gas. A 3rd small N 2 stream was passed through an oleum solution to saturate the
stream with SO 3.

Table 1A shows initial experiments at undefined residence times around 1 second,

where these three streams were added and let to react at controlled temperatures in
the 300-400 °C interval.
The outlet from the reaction chamber was analyzed for content of elemental sulfur, sul-
furic acid (=SC>3 reacted with H2O in the gas) and SO2. The results shown in Table 1A
show that there is some gas phase reaction taking place between SO3 and H2S, but
also that the reaction is relatively slow and not sufficiently fast to ensure complete SO3
destruction in an industrial Claus process plant.

Table 1A:

Table 1B shows additional experiments at controlled residence times, where these

three streams were added and let to react at controlled temperatures at 350 °C with re-
action chamber residence times of 0.4 second to 1 second.

The results shown in Table 1B also show some gas phase reaction taking place be-
tween SO3 and H2S, but also that the gas phase reaction is relatively slow and not suf-
ficiently fast to ensure complete SO3 destruction in an industrial Claus process plant.
Contrary to this fast and near complete SO3 destruction is possible by application of a
catalyst.

Inspection of the materials have indicated that the SO3 removal over alumina may be
due to sulfation of the alumina, rather than a catalytic conversion. Such a sulfation may
however still be of commercial relevance, if an amount of alumina is used as guard ma-
terial, since the subsequent Claus catalyst is protected from deactivation by SO3.
Table 1B :

Example 2

The chemical reactions taking place in the Claus reaction furnace are numerous and
have been calculated using a very detailed kinetic model including more than 50 chem-
ical species and more than 1000 chemical elementary reactions, each reaction de-
scribed with a temperature dependent rate constant.

The model has been used to calculate both the kinetics of the Claus reaction furnace
and the chemical equilibrium of the Claus reaction furnace mixture, i.e. the model was
used to predict whether the sulfuric acid feed would react completely with the S in
the reaction furnace.

The acid gas feed to the Claus reaction furnace consisted of 9 1 .4 vol% S , 2.1 vol%
CO 2 , 3.3 vol% H2O , 1 .4 vol% C H4 and 1.9 vol% H2, representing a concentrated acid
gas from e.g. a refinery process.

The sulfuric acid was 93 %w/w H2SO4, representing a concentration of the sulfuric acid
product from a wet type sulfuric acid plant installed as a tail gas treatment plant down-
stream the Claus process plant. The sulfuric acid flow accounted for 9.8 % of the total
sulfur input to the Claus reaction furnace.

The reaction temperature was 1050 °C and the pressure 1.65 bar absolute.
Figure 3 shows that the chemical reactions in the Claus reaction furnace are very fast
and in less than 0.5 seconds chemical equilibrium is achieved, i.e. the composition of
the process gas does not change.

However, the kinetic model only includes gas phase species and the time needed for
the evaporation of sulfuric acid droplets have not been included. If the evaporation of
the droplets is achieved in less than 0.5 seconds, the process gas from the Claus reac-
tion furnace (with 1 second residence time) will be substantial SO3 free and the opera-
tion of the Claus process plant will be unproblematic. However, if the evaporation of
some of the droplets takes more than 1-2 seconds, the reaction furnace off gas cannot
be considered SO3 free and unproblematic Claus process plant operation is not guar-
anteed.

In such a situation, the newly developed material catalytically active in reducing S O 3

(and H2SO4) by reaction with H 2 S is necessary for long operation of the Claus process
plant.
Claims

1. A process for production of sulfur from a feedstock gas comprising from 30

vol%, from 40 vol% or from 50% to 99 vol% or to 100 vol% H2S and a stream
of sulfuric acid involving the steps of
a . providing a Claus reaction furnace feed stream comprising said feedstock
gas, an amount of sulfuric acid, an amount of molecular oxygen and op-
tionally an amount of fuel, wherein the amount of molecular oxygen is
substoichiometric,
b. directing said Claus reaction furnace feed stream to a Claus reaction fur-
nace, providing a Claus reaction furnace off gas,
c . cooling said Claus reaction furnace off gas to provide a cooled Claus re-
action furnace off gas and optionally withdrawing elemental sulfur from the
gas
d . directing said cooled Claus reaction furnace off gas to contact an S O 3
guard material, absorbing and/or converting S O 3 , providing a substantially
S O 3 free Claus converter feed gas

e . directing said SCh free Claus converter feed gas to contact a material cat-
alytically active in the Claus reaction,
f . withdrawing elemental sulfur, optionally by cooling the effluent from said
material catalytically active in the Claus reaction,

characterized in said SO 3 guard material being different from said material

catalytically active in the Claus reaction.

2 . A process according to claim 1, wherein the S O 3 guard is an S O 3 absorbent,

in which the content of S O 3 is increased over time, such as alumina or titania.

3 . A process according to claim 1, wherein the S O 3 guard material is a material

catalytically active in reducing S O 3 by reaction with H 2S , providing a substan-
tially S O 3 free Claus converter feed gas.

4 . A process according to claim 1, 2 or 3 , wherein the S O 3 guard material is ar-

ranged downstream the Claus reaction furnace and upstream the Claus con-
verter.
 5 . A process according to claim 1, 2 , or 3 , wherein the SO 3 guard material is ar-
ranged as top layer on material catalytically active in the Claus reaction.

6 . A process according to any one of claims 3 , 4 or 5 , wherein the material cata-

lytically active in the reduction of SO 3 comprises one or more elements taken
from the group consisting of V , Mn, Fe, Co, Cu, Zn, Ni, Mo, W, Sb, T i and Bi
and a support comprising one or more elements taken from the group con-
sisting of Al, Ti, Si, Zr, and Mg.

7. A process according to claim 6 , wherein the support comprises diatomaceous

earth and/or cordierite.

8 . A process according to any one of claims 1 to 5 , wherein the material active

in the reduction of SO3 is in shape of pellets or a monolith.

9 . A process according to any one of claims 1 to 6 , wherein the Claus reaction

furnace is operated at a temperature of between 900 and 1500°C.

10. A process according to any one of claims 1 to7, wherein the material catalyti-
cally active in reducing SO3 is operated at a temperature of between 130 and
1500°C.

11. A process according to any one of claims 1 to 8 , wherein the material catalyti-
cally active in reducing SO3 is operated at a temperature of between 250 and
500°C.

12. A process according to any one of claims 1 to 9 , wherein the material catalyti-
cally active in reducing SO3 is operated at a temperature of between 300 and
400°C.
13. A process according to any one of claims 1 to 10, wherein the stream of sul-
furic acid is produced in a wet type sulfuric acid plant treating the tail gas from
the Claus plant.
 INTERNATIONAL SEARCH REPORT
International application No

PCT/ EP20 19/079233

A . CLASSIFICATION OF SUBJECT MATTER
I NV . C0 1 B 17/04 B0 1D53/86 B0 1J20/06
ADD .

According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
C0 1 B B0 1 D

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO - I nterna l , WP I Data

 INTERNATIONAL SEARCH REPORT
International application No

PCT/EP2019/079233
C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Cat tat ion of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

X US 6 056 936 A (NOUGAYREDE JEAN [FR] ET 1-13

AL) 2 May 2000 (2000-05-02)
col umn 2 , l i ne 1 1 - l i ne 14
col umn 2 , l i ne 3 7 - col umn 3 , l i ne 1
col umn 4 , l i ne 29 - col umn 5 , l i ne 53
col umn 8 , l i ne 3 1 - l i ne 6 1
exampl e s 4,5

X WO 2015/022524 A 1 ( LINDE A G [DE] ; SETNA 1-13

ROHAN P [GB] )
19 February 2015 (2015-02-19)
page 4 , l i ne 16 - page 5 , l i ne 12
page 8 , l i nes 7-12
page 10, l i ne 15 - page 1 1 , l i ne 2
page 13 , l i nes 7-28
page 14, l i nes 7-19

X US 9 023 309 B1 (RAMESHNI MAHIN [US] ET 1-13

AL) 5 May 2015 (2015-05-05)
col umn 5 , l i nes 13-16
col umn 8 , l i ne 7 - l i ne 29
col umn 9 , l i ne 55 - l i ne 64

X GB 2 087 373 A (ELF AQUITAINE) 1-13

2 6 May 1982 (1982-05-26)
page 1 , col umn 1 , paragraph 2 - col umn 2
paragraph 2
page 2 , col umn 2
exampl e 1

X CN 108 525 672 A (JIANGSU TIANDONG NEW 1-13

MATERIAL TECH CO LTD)
14 September 2018 (2018-09-14)
exampl e s 5 , 6

Form PCT/ISA/210 (continuation of second sheet) (April 2005)

 INTERNATIONAL SEARCH REPORT
International application No
Information on patent family members
PCT/EP2019/079233
Patent document Publication Patent family Publication
cited in search report date member(s) date

WO 2017220655 A1 28-12-2017 EP 3472096 A1 24-04-2019

WO 2017220655 A1 28-12-2017

US 6056936 02-05-2000 AT 188673 T 15-01-2000

CA 2196103 A1 05-12-1996
CN 1155874 A 30-07-1997
DE 69606145 D1 17-02-2000
DE 69606145 T2 21-09-2000
DK 0772569 T3 26-06-2000
EP 0772569 A1 14-05-1997
ES 2143763 T3 16-05-2000
FR 2734809 A1 06-12-1996
JP 3766100 B2 12-04-2006
JP H10504795 A 12-05-1998
NO 320320 B1 21-11-2005
RU 2142402 Cl 10-12-1999
TW 402521 B 21-08-2000
US 6056936 A 02-05-2000
WO 9638378 A1 05-12-1996

WO 2015022524 A1 19-02-2015 BR 112016002898 A2 01-08-2017

CA 2920747 A1 19-02-2015
CN 105452157 A 30-03-2016
EP 3033301 A1 22-06-2016
GB 2517161 A 18-02-2015
IL 244035 A 29-03-2018
KR 20160041943 A 18-04-2016
RU 2016106628 A 18-09-2017
UA 118970 C2 10-04-2019
US 2016167964 A1 16-06-2016
WO 2015022524 A1 19-02-2015
ZA 201601626 B 31-05-2017

US 9023309 B1 05-05-2015 NONE

GB 2087373 26-05-1982 CA 1166823 A 08-05-1984

DE 3145642 A1 12-08-1982
FR 2494255 A1 21-05-1982
GB 2087373 A 26-05-1982
IT 1144930 B 29-10-1986
JP S57111208 A 10-07-1982
NL 8105179 A 16-06-1982
NO 158215 B 25-04-1988
SU 1248531 A3 30-07-1986
US 4436716 A 13-03-1984

CN 108525672 A 14-09-2018 NONE