Dear Rashidul,

Good afternoon. I was deeply studying the CRU startup manual of AXENS, UOP &
SINOPEC and was comparing them side by side to get an effective way of plant startup
by taking account of existing plant facilities. I have compiled all discrete information and
have prepared a summary of alternate start up biography for ARL. I would like to
forward it for your acknowledgement and information sharing. We may also seek
expert’s comments on these findings for further clarification so that at the end
even better idea can come out.

Alternate start up biography of ARL:

Startup idea 01 (Feeding HSR naphtha of 85C –165C directly in CRU):

a. Limit of sulfur in CRU feed is as follows:
As per AXENS <= 0.2 ppm
As per UOP/ SINOPEC <= 0.5 ppm

b. For NHT pre-sulfiding either in once-through or recycle manner, as per SINOPEC

literature 1600 kg of DMDS is required which is a 24-hour process. If HSR
naphtha of 85C –165C (Consisting of 30 to 100 ppm S) is directly charged into
CRU to produce H2 and then supplying it to NHT pre-sulfiding a theoretical
calculation significantly need to ask from SINOPEC. They need to tell us how
long time their CRU catalyst will survive by taking severe upset feed even we run
the unit to its 50% of design capacity. If the catalyst last more than 24 hr. we can
take that risk charging high “S” content feed to CRU catalyst by compromising
the first cycle length of catalyst.
c. If the catalyst last less than 24 hours, it will be wise not to take that risk
considering following points:
 To restore the activity of CRU catalyst, regeneration is needed which is a
long and troublesome process.
 SINOPEC literature says SR-1000 catalyst has a proprietary ex-situ
regeneration process.
 SINOPEC literature also says during regeneration Gas/ Catalyst volume
ratio = 800-1500 Nm3/ m3.hr which means that total H 2 requirement during
regeneration is 8000-15000 Nm3 (N.B: CRU Catalyst volume is 10m 3)
whereas our H2 storage capacity is 4500 Nm3. Moreover, we do not have
DSN to charge in CRU catalyst to restore its activity by removing “S” from
Pt and Rh.
 Axens Operating Instructions says “The reformer catalyst responds
within minutes of poisoning with sulfur, indicated by a shift in
reactor Delta T and product yield loss”
  None of our team member who has come from Petromax has the catalyst
regeneration experience as until now Petromax has not regenerated their
CRU CATALYST (RG- 682).

Startup idea 02 (NHT Pre-sulfiding with DMDS by recycle mode of

compressor and using existing hydrogen from hydrogen storage
tanks):
 By using existing stored hydrogen (4000Nm 3) we can take an attempt, which is
starting NHT first. NHT catalyst will be sulfided by recycle mode instead of once
through mode of compressor K-3001. In this 24 hour sulfiding process maximum
sulfur content will be 5000 ppm in the recycle gas. We know Ariel Piston, Con.
Rod, piston rod etc. are designed for low corrosive service (i.e. 200 -600 ppm S).
If we take our compressor under this harsh 24 hr corrosive service our
compressor parts will not definitely brake as we are not changing the gas load on
piston by handling other kind of heavier gases like N 2, Ammonia, CO2 instead of
handling H2. Exceptionally what maximum can happen is a minor corrosion may
occur or even may not occur as the compressor H 2S exposer time is only 24
hours.
 We may take idea from Ariel in this regard.
 SINOPEC told in their literature to maintain H2 purity above 80% during sulfiding
in once through manner of compressor. As Startup idea 05 is sulfiding catalyst by
recycle mode of compressor and our H2 reserve is small (only 4000 Nm3) it will
be advantageous for us if we are allowed by SINOPEC to keep H2 purity above
50% during sulfiding. This may reduce make up H 2 requirement. (Ref: Axens
allowed 50%. H2 purity during pre-sulfiding)
 We have to do an exact calculation on “finishing NHT Pre sulfiding
possibility” by using existing H 2 reserve. It is more important because
based on it the startup ideas 2 prevails.
 H2 will be consumed during NHT Pre sulfiding at the same time H2 will be
accumulated in the storage from H2 generator to run CRU next. This H 2
accumulation may roughly take additional one month.

Startup idea 03 (Feeding HSR Naphtha directly to NHT catalyst

without catalyst sulfiding):
As per this idea, HSR Naphtha will be feed directly to NHT catalyst without sulfiding
when the reactor bed temperature will raise 260-280C. The product after NHT reactor
will be taken to NHT stripping column. It will be then tested to check “S” quantity. If the
value get down below 10 ppm we then send the stripper bottom product to CRU.
 Comparison between start up Ideas 2, 3:
Startup Idea Price Lead Time Comments
Idea 02 N/A N/A Need to do an exact calculation that NHT
Pre sulfiding is possible by using existing
H2 reserve on recycle mode of compressor.
Idea 03 N/A N/A We are not sure about “S” content in the
stripper bottom product. It may 10ppm or
even more. Chance is 50/50.

Startup idea 04 (Regenerative Non Regenerative adsorbent):

a. It will reduce our dependency on DSN to start CRU from each shut down of the
plant as HSR Naphtha can directly charge to CRU through adsorbents.
H2 produced from CRU will be used later to start NHT and all heaters.
b. No need to store DSN in the tank all time as a dead stock.
c. It will reduce our dependency on H2 from H2 generator during each startup.
d. Adsorbent both regenerative as well as non-regenerative type are available.
e. Adsorbent reduces “S” content from liquid hydrocarbon stream bellow 0.5
ppm. One more point need to recheck precisely that, can the adsorbent
(both regenerative and non-regenerative) shrink sulfur content from 100
ppm to 0.5 ppm as “S” varies from 30- 100 ppm in feed.
f. We may search refurbish vessel from Chittagong ship yard as an adsorbent
vessel. It will save vessel manufacturing and shipment time.

Startup idea 05 (DSN Procurement):

For stable operation of CRU, SINOPEC literature says 7 days DSN should be reserved
which is 2500 MT or 33,00,000 Lit. which will cost us almost 28 crore (considering
85tk/Lit DSN).

STARTUP SEQUENCE:

DSN> CRU> H2 > NHT STARTUP

Startup idea 06 (Procurement of NHT Pre sulfided catalyst):

We can swing existing 2.62 ton NHT non-sulfided catalyst with NHT Pre-sulfided
catalyst. Then we will feed HSR naphtha directly to Pre-sulfided catalyst which will
produce DSN. After that CRU will be operated.

STARTUP SEQUENCE:
HSR naphtha> NHT > DSN> CRU> H2 > All heater firing.

Existing 2.62 ton NHT non-sulfided catalyst will be used later when Pre-sulfided catalyst
will lose its activity by trailing regeneration ability.RS-1 is regenerate-able catalyst
whereas the NHT guard catalyst RG-1 is non-regenerate able.

Comparison among start up Ideas 4, 5, 6:

Startup Idea Price Lead Time Comments

Idea 04 adsorbent Less than 8 crore Low (Considering Air Price of Petromax
(based on freight) NHT CRU catalyst
Assumption) was 8,20,000 euro or
8 crore
Idea 05 DSN About 28 crore High (Considering 2500 MT or
(33,00,000 Lit) sea freight from 33,00,000 Lit.
Singapore, Vietnam,
India, Gulf etc.)
Idea 06 NHT Pre Less than 8 crore Low (Considering Air Price of Petromax
sulfide catalyst (based on freight) NHT CRU catalyst
Assumption) was 8,20,000 euro or
8 crore

Brief CRU Feedstock Properties:

Heavy straight run naphtha (HSR) of boiling range from 85OC-165OC is the desired
Reformer feed. Light straight run Naphtha (LSR C5-85OC) is undesirable as it tends to
cracked to gas. On the other hand hydrocarbon boiling point above 180C is easily
hydrocracked resulting in excessive carbon which promotes catalyst deactivation by
coke deposition on catalyst pore. The optimal feedstock to a reformer with respect to H 2
yield is C6-C9 cut which contains highest naphthene concentrations. No H 2 can be
produced from C5 fraction and little H2 is produced from C10+ which are highly
susceptible for hydrocracking so as to gum formation.

Petromax (Axens recommended CRU cut )= 95C-160C

SINOPEC recommended CRU cut= 85C -165C

Source of Sulfur in the Naphtha feed:

In Naphtha the principle sulfur compounds include mercaptans, aliphatic sulfides,

aliphatic disulfides and five and six membered ring cyclic sulfides. Thiophenes are
found typically in heavier cracked naphthas but are not usually present in straight run
naphthas. Under the pretreater reactor conditions these sulfur compounds react readily
to produce the corresponding saturated compound, releasing H 2S.
CH3 - CH2 - CH2 - CH2 - CH2 - SH + ® C5 H12 + H2S
H2
Amyl Mercaptan n-pentane

Desulfurization of the ring implies the opening of the ring and its simultaneous
hydrogenation.
XMercaptane Carbon Boiling Sulfides Carbon Boiling
Chain point(C) Chain point(C)
Methyl mercaptane CH4S 6 Dimethyl Sulfide C2H6S 37.3
ethyl mercaptane C2H6S 35 Diethyl Sulfide C4H10S 92
pthyl mercaptane C3H8S 68 Dipropyl Sulfide C6H14S 142
Buthyl mercaptane C4H10S 98 Dibutyl Sulfide C8H18S 189
Penthyl mercaptane C5H12S 127 Hydrogen Sulfide H2S -60
Hexyl mercaptane C6H14S 151 Dimethyl Disulfide C2H6S2 110
Hepthl mercaptane C7H16S 175      
Octyl mercaptane C8H18S 199      

Thiophene Carbon Boiling Sulfers    

Chain point(oC)
methyl thiophene C5H6S 113 Mercaptans RSH+H2 RS+H2S
Ethyl thiophene C6H8S 133 sulfides R2S+2H2 2RS+H2S
Prophyl thiophene C7H10S 160 Disulfides (RS)2+3H2 2RH+2H2S
2,4-Dithiopentane C3H8S2 147 Thiophene HC-CH  
1,3-Propanedithiol C3H8S2 169   HC-CH C4H10+H2S
        S  

(Courtesy: Mr. Jagadish Ghosh )

Due to this different boiling points of different mercaptane and sulfides compound the
ultimate “S” content in HSR naphtha at ppm level differs from IBP to EBP. It generally
varies from 30 to 100 ppm.