Refining-Petrochemicals-Chemicals-Engineering

PDVSA

Process Engineering Applied To Petroleum Refining Module 8: REFINING PROCESSES (2)

VACUUM DISTILLATE HYDROCRACKING

I - PURPOSE OF HYDROCRACKING AND INTEGRATION WITH IN THE REFINING SCHEME ................................................................................................................. 1 II - PROCESS CHARACTERISTICS .............................................................................................. 8
1 2 3 4 Chemical reactions .......................................................................................................................8 Hydrorefining catalysts ...............................................................................................................10 Hydrocracking catalysts .............................................................................................................10 Main catalyst constraints ............................................................................................................ 14

III - HYDROCRACKER OPERATING CONDITIONS ................................................................... 15

1 2 3 4 5 6 Feed circuit .................................................................................................................................15 Reactor section .......................................................................................................................... 15 Refrigeration - HP and MP separators ....................................................................................... 15 Distillation section.......................................................................................................................16 Hydrocracking catalyst activation ...............................................................................................16 Catalyst regeneration .................................................................................................................16

IV - HYDROGEN PRODUCTION ................................................................................................... 18

1 2 Principle of the reaction.............................................................................................................. 18 Hydrogen production plant .........................................................................................................19

RA HCR - 00111_A_A - Rev. 2

17/01/2005

2005 ENSPM Formation Industrie - IFP Training

I-

PURPOSE OF HYDROCRACKING AND INTEGRATION WITHIN THE REFINING SCHEME

Distillate hydrocracking is a sophisticated conversion process that simultaneously involves heat, several types of specific catalysts and the addition of hydrogen to promote and control heavy hydrocarbon cracking reactions. It is characterized by significant upgrading of heavy feeds that are converted largely into high quality light and intermediate products. Unlike other conversion processes, hydrocracking has the additional advantage of offering considerable operating flexibility which makes it possible to a certain extent to adapt unit production to market requirements. A typical material balance at total conversion and main product characteristics, are shown below.

PRODUCTS INPUT Distillate feed Hydrogen TOTAL INPUT OUTPUT

YIELDS % wt of feed

REMARKS

100 3 103.0

Catalyst constraints: limited metal, nitrogen, Conradson carbon residue content Substantial consumption of hydrogen requiring production plant

Gas (H 2S, C 1, C 2, C 3, NH3) Butane Light gasoline Heavy gasoline Kerosene Gas oil TOTAL OUTPUT 4.3 4.6 14.1 18.0 38.0 24.0 103 -

sulfur plant required for H2S treatment process water stripping

Rich in isoparaffins, high RON Rich in N - Excellent RON after reforming Requires appropriate reforming capacity Good cold condition characteristics - Sulfur-free High cetane number - Sulfur-free

This example shows: - the excellent process selectivity with respect to gasoline, kerosene and gas oil fractions - the absence of heavy products as produced by FCC - the substantial hydrogen consumption

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2005 ENSPM Formation Industrie - IFP Training

COMPARISON FCC/HYDROCRACKING

Catalytic cracking Operating conditions H2 Total pressure Temperature (C) Cycle duration (between two regenerations) Contact time No 1 bar 500-600 A few seconds A few seconds Product quality Gasoline Gas oil Base oil Relatively good Very poor (CN 20) Insuitable Feed processed VR + e AR

Hydrocracking

Yes > 100 bar 350-430 1 to 3 years 1 hour

Poor Excellent (CN > 55) Excellent (VI > 110)

Vacuum distillate

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STRUCTURE OF THE PRODUCT YIELDS OBTAINED BY THE DIFFERENT CONVERSION PROCESSES

Ranking of product quality

++ very good + good - poor -- very poor

F. C. C.
0 10 20 %

GAS + LPG

VGO from crudes

FCC FEEDS

30 40 50 60 70 LCO 80 Gasolines

VGO from visbreaker etc.

100

Coke* * self consumed

HYDROCRACKING
0 10 20 30 Gasoline Heavy ++
GAS + H2S

+ Light *

FEEDSTOCKS

VACUUM DISTILLATES 360 - 350C

50 60 70 80 360 90 100

Kerosene

++

Gas oil

++
D PCD 343 B

102.5

*
00111_A_A

After catalytic reforming

2005 ENSPM Formation Industrie - IFP Training

PRODUCTS

40

D PCD 334 C

90

HCO + Slurry

P R O D U CT S

Vacuum residues with low metal content

+ or

SINGLE STAGE

ONCE THROUGH OR RECYCLE WITH ONE OR TWO REACTORS (HDT-HDC)

D PCD 1173 A

00111_A_A

HYDROCRACKER CONFIGURATION : SINGLE STAGE - TWO STAGE

CRACKING REACTION AND HYDROCRACKING CONFIGURATION

CUT

VGO

Gas-oil Kero Naphtha C16 C8

Gas

number of Caverage

C32

C4

2005 ENSPM Formation Industrie - IFP Training

USA Maxi naphtha objective TWO STAGE (NH3-H2S removed after first stage)

Outside USA Maxi gas oil objective

Series flow once through Zeolite cracking catalyst

Series flow with liquid recycle

D PCD 2100 D

00111_A_A

Single-stage once through

Single-stage with liquid recycle

Amorphous silica-alumina catalyst

SINGLE-STAGE

2005 ENSPM Formation Industrie - IFP Training

TYPICAL HYDROCRACKING PROCESS Flow schemes

One-stage process

Make up H2

H2 recycle 1 or 2 REACTORS

FRACTIONATION LPG

NAPHTHA FRESH FEED MIDDLE DISTILLATES

SEPARATION FUEL OIL RESIDUE RECYCLE

Two-stage process

Make up H2 1st STAGE REACTOR FRESH FEED

H2 recycle FRACTIONATION LPG

NAPHTHA 2nd STAGE REACTOR MIDDLE DISTILLATES

SEPARATION FUEL OIL RESIDUE RECYCLE

00111_A_A
D PCD 1174 B

2005 ENSPM Formation Industrie - IFP Training

D PCD 1174 A

The incorporation of the hydrocracking process within the refining scheme requires a complex that includes the following units: - a specific vacuum distillation unit allowing separation of distillate feeds that meet purity specifications with respect to metals, Conradson carbon residue, etc. - a hydrogen production plant using the steam reforming process which enables hydrogen production from light hydrocarbons (methane, fuel gas, butane, etc.) - a hydrocracking unit, consisting of a reaction section operating at high pressure (around 160 bar) and high temperature (360-400C) and a complex separation section - a sulfur plant including facilities for amine washing of gaseous effluent for H 2S recovery and for sulfur production - a stripper for process water which contains large amounts of ammonia and H2S A typical hydrocracker flow scheme is shown below.

LIGHT HYDROCARBONS WATER GAS WATER STRIPPER HYDROGEN STEAM PRODUCTION UNIT (steam reforming) HYDROCRACKING HYDROGEN Reaction Separation WATER GAS

SULFUR UNIT H 2S AMINE WASHING

SULFUR

FUEL GAS

PROPANE BUTANE LIGHT GASOLINE HEAVY GASOLINE TO REFORMER KEROSENE GAS OIL RECYCLE

GAS OIL ATMOSPHERIC RESIDUE VACUUM DISTILLATION DISTILLATE

VACUUM RESIDUE

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2005 ENSPM Formation Industrie - IFP Training

D PCD 1172 A

The hydrocracking process does not enable separation of the distillate feed into light and intermediate products in one run. The conversion per run is therefore determined as the ratio of gas oil and lighter products (370C) obtained to the feed rate. Conversion per run = 370 product rate x 100 feed rate

and the normal value is in the range of 60 - 70%. Consequently the fraction heavier than gas oil has to be recycled to the reaction section, which obviously reduces the amount of fresh feed that can be run.

II -

PROCESS CHARACTERISTICS 1CHEMICAL REACTIONS

The operating conditions used in hydrocracking processes: - temperature of 360 - 400C - high hydrogen pressure - use of hydrorefining and hydrocracking catalysts result in complex chemical reactions that can, for the sake of simplicity, be classified under the following three headings: conventional hydrorefining reactions, hydrogenation reactions and actual hydrocracking conversion reactions. a - Hydrorefining reactions They are similar to the chemical conversions already encountered in conventional hydrotreating. Due to the severity of operating conditions the reactions are virtually complete, resulting in highly purified products. The reactions involve heavy compounds of sulfur, nitrogen and oxygen and lead to the formation of H2S, NH3, H 2O and light products. Sulfur, nitrogen and hydrogen compounds + hydrogen H 2S NH3 H 2O saturated, lighter hydrocarbon compounds

These reactions are exothermic and moderately hydrogen consuming. One important property is their removal of heavy nitrogen compounds which are poisons for acid hydrocracking catalysts. The effectiveness of hydrorefining reactions obviously depends on the amount of sulfur and nitrogen impurities in the distillate feedstock.

00111_A_A

2005 ENSPM Formation Industrie - IFP Training

b - Hydrogenation reactions The degree of hydrogen pressure used in hydrocracking processes combined with the hydrogenating properties of the catalysts results in virtually complete hydrogenation of the unsaturated chemical compounds. This applies in particular to aromatic hydrocarbons and explains at the same time why hydrocracked products are largely composed of saturated paraffinic and naphthenic hydrocarbons. A typical chemical equation of the hydrogenation of a heavy aromatic compound is shown below.

+ hydrogen

Heavy aromatic hydrocarbon

heavy naphthenic hydrocarbon

It leads to the formation of naphthenic hydrocarbons. Hydrogenation reactions are very exothermic and hydrogen consuming. c - Hydrocracking reactions They are an essential factor in this conversion process because they lead to the formation of products lighter than those in the feed. They apply to all types of hydrocarbons. heavy hydrocarbons P, N or A + H2 light hydrocarbons

For example C 30H62 + H2 C 15H32 + C 15H32

The amount of hydrogen consumed is equivalent to the degree of saturation of the short molecules cracked. At the same time these reactions are very exothermic. It should be noted that the action of the catalyst in this process is to orient the shortest paraffinic molecules produced toward isomerized forms. This explains the high octane number of the light gasoline. OVERALL it can be seen that the DIFFERENT CHEMICAL REACTIONS involved in the hydrocracking process are all hydrogen consuming, which explains the high input of this component in the material balance of the unit. Another common factor is the exothermic nature of the reactions, which means that precautions have to be taken to avoid any runaway of the reaction section.

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2005 ENSPM Formation Industrie - IFP Training

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2-

HYDROREFINING CATALYSTS
The first stage of the hydrocracking process is similar to conventional hydrotreating and uses hydrorefining catalysts not very different from those used in hydrodesulfurisation of kerosene and gas oil. These catalysts are of the NiMo type and are composed of an alumina support bearing active nickel and molybdenum sulfides. They promote desulfurisation and denitrogenation, and also hydrogenation . They are used in the first reactor, known as the HYDROREFINING REACTOR, designed to hydropurify the feed before it undergoes the actual cracking process. Typical operating conditions for the first reactor are as follows: Pressure Temperature Catalyst Exothermicity : : : : 160 bar, chiefly due to hydrogen approximately 375C NiMo on alumina hydrogen quench between the two beds

At the reactor outlet the reaction mixture is therefore composed of the hydropurified and partially hydrogenated feed, hydrogen, and H2S, NH3 and H 2O formed by the chemical reactions.

3-

HYDROCRACKING CATALYSTS
Like the catalytic reforming process, hydrocracking requires dual-purpose catalysts that are used in a second reactor called the CONVERSION REACTOR. The catalysts must simultaneously satisfy the following requirements: - they must promote cracking reactions, which calls for an acid catalyst. Synthetic silicaalumina catalysts are amorphous (non-crystalline) solids with acid properties and have been widely used in cracking processes. they have currently been replaced, however, by crystalline silica-alumina systems called ZEOLITES which are significantly more acidic. - they must possess hydrogenating properties to be able to hydrogenate the heavy hydrocarbons in the feed and to saturate the cracked species with hydrogen. This action can be provided by sulfide combinations of the NiMo or NiW type and in some formulations even by precious metals such as palladium. The fundamental property of hydrocracking catalysts probably lies in the acidity of the silica-alumina support. It is the acid support that is directly subject to the poisonous action of the alkaline nitrogen compounds not converted in the refining reactor, and of ammonia.

00111_A_A

2005 ENSPM Formation Industrie - IFP Training

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The basic pattern of the silica-alumina structure is a tetrahedron. The four peaks of the tetrahedron are occupied by oxygen atoms (valence = 2) and the centre by a silicon atom (valence = 4) or by an aluminium atom (valence = 3). These two basic patterns are shown below.

Oxygen Si

Ngative charge AI
D CH 1000 C

Basic patterns of silica-alumina structures

As can be seen, due to the tri-valence of the aluminium atom, the tetrahedron in question has a residual negative charge. Assembly of the elementary tetrahedra is based on the valence of the oxygen atoms that remains free. The tetrahedra may be assembled by their peaks, by their surfaces or by their edges, resulting in a random assembly in space. This leads to a structure of varying porosity, characteristic of AMORPHOUS or non-crystalline silica-alumina. The figure below shows a portion of such an assembly.

Na+

Na+ Al Na+ Si Al

Si

Si

Al

Si

Si

Na + Al Si Si Al

Na +

Positively charged sodium ions Na+ appear in the structure to compensate for the negative charges due to the presence of aluminium atoms in the silica-alumina. Acidity is achieved by an acid treatment that replaces the Na+ ions by H+ ions.

00111_A_A

2005 ENSPM Formation Industrie - IFP Training

D CH 1000 B

12

ZEOLITES or MOLECULAR SIEVES are silica-alumina systems that have a specific crystalline structure. There are a great variety of them but the basic element is always the same SiO 4 or AlO4 tetrahedron. Unlike the amorphous silica-alumina systems, these elementary tetrahedra assemble exclusively by their peaks, which produces the basic crystalline pattern (known as sodalitic pattern) of the zeolites used in acid catalysis.

In the figure all the oxygen, silicon and aluminium atoms are shown. To simplify the sodalitic pattern and make it easier to see, first all the oxygen atoms not located on the edges are removed (a), and then only the silicon and aluminium atoms are shown (b).

(a)

D CH 306 A

(b)

Sodalitic pattern

The polyhedron has 6 square surfaces and 8 hexagonal surfaces. The structures are assembled either by the square surfaces or by the hexagonal surfaces.

00111_A_A

2005 ENSPM Formation Industrie - IFP Training

D CH 303 A

13

Assembly by the square surfaces: A SIEVE These assembled structures are repeated in space and produce very regular, interconnected cavities which give the solid a very specific crystalline structure.

Location of "cages"
Lattices assembled by their square faces
D CH 146 B

Assembly by the square surfaces The openings to the cavities in the A sieves vary from 3 to 5 , in size according to the nature of the positively charged ions incorporated in their structure. A-type sieves are used in industry for gas purification (drying) or for separating the constituents of a mixture according to the size of their molecules, hence the term molecular sieves. Assembly by the hexagonal surfaces: X or Y SIEVES (according to the proportions of silicon and aluminium)

Hexagonal face lattice assembly

00111_A_A

Assembly by the hexagonal surfaces 2005 ENSPM Formation Industrie - IFP Training

D CH 147 B

14

Assembly by the hexagonal surfaces produces cavities of larger volume and openings exceeding 10 . This crystalline structure of X or Y sieves is therefore more suited to the adsorption of heavy hydrocarbon molecules which in addition can circulate within the zeolite due to the interconnecting cavities. At the same time the ion exchange that acidifies the sieves gives them much greater acidity than the amorphous silica-alumina systems which explains why they are used for hydrocracking. Typical conversion reactor operating conditions are as follows: Pressure Temperature Catalyst : : : 160 bar approximately

360 - 400C
3 beds of hydrocracking catalyst 1 bed of hydrorefining catalyst hydrogen quench between the second and third bed

Exothermicity control :

The use of the last hydrorefining catalyst bed is to remove the sulfur compounds that may have formed due to the action of H2S on the intermediate products of the reaction.

4-

MAIN CATALYST CONSTRAINTS

a - Constraints connected with the feed. They concern - nitrogen compounds and ammonia which de-activate the catalyst. This requires an increase in the temperature or reduction of the feed rate in order to obtain the desired conversions - sulfur. Concentration of H2S should be within a bracket that ranges from a minimum value necessary to maintain the sulfur forms of the active species to a maximum value beyond which catalyst activity deteriorates - metals , concentration of which is strictly limited. An initial amount is nevertheless removed by the hydrorefining catalyst - asphaltenes and resins that may be entrained in vacuum distillation and are coke promoters. Conradson carbon residue is related to these compounds b - Constraints connected with operating conditions - moderate temperature to avoid excessive coking of the catalyst - very high H2/HC ratio for the same reason as above - large amount of catalyst in relation to the feed rate to ensure a sufficiently long catalyst-feed contact time.

00111_A_A

2005 ENSPM Formation Industrie - IFP Training

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III - HYDROCRACKER OPERATING CONDITIONS (Figure 1) 1FEED CIRCUIT

The feed circuit includes a pump capable of raising the pressure of the liquid distillate feed to a value higher than that of the process, and heat exchangers allowing recovery of heat from the hot effluents from the reaction section. The first reactor inlet temperature is controlled by a mixture of hydrogen-rich gas which is over 90% pure. The hydrogen alone is heated in a furnace controlled by the reactor inlet temperature. This avoids risks of coking. The latter is liable to occur if the feed is heated directly in the furnace. Hydrogen pressure on the catalyst in the reactor is determined by hydrogen dilution. It is calculated in m3 of pure hydrogen per m3 of feed. The design value is in the region of 750 - 800 m 3 /m3 .

2-

REACTOR SECTION
The refining reactor includes two catalyst beds. A rise in temperature is observed in the first bed due to the exothermic hydrorefining and hydrogenation reactions. A hydrogen quench lowers the temperature before the feed is subjected to the second bed, bringing it more or less to the first reactor inlet temperature. The rise in temperature in the second bed is again the result of the exothermicity of the reactions. At the first reactor outlet the recycle is added to the mixture. The injection of hot hydrogen regulates conditions at the conversion reactor inlet, i.e. a slightly higher temperature than in the first reactor and greater dilution (approximately 1200 m3 H2/m3). The exothermicity of the hydrocracking reactions results in a difference in temperature ( Dt) between the inlet and outlet of the 3 beds. Temperatures are controlled by two hydrogen quenches. The reactors operate at the pressure required by the process (around 160 bar). The differences in pressure between inlet and outlet are due to pressure drops in the mixture as it moves through the reactor. Pressure drops increase with catalyst coking, fouling and plugging.

3-

REFRIGERATION - HP AND MP SEPARATORS

At the second reactor outlet the mixture of hydrogen and cracked products is cooled by heat exchange with the feed, the hydrogen and the liquid effluent of the MP separator. Condensation is completed by air coolers upstream of the HP separator. It should be noted that injection of process water before the air coolers can prevent condensation to solid state of salts such as ammonium sulfide formed by the action of H2S or NH3. Figure 2 indicates the conditions for formation of solid ammonium sulfide. The separator is maintained at 160 bar and separates: - a gas phase rich in hydrogen to which is added make-up hydrogen from the hydrogen plant via the make-up compressors. The resulting mixture is compressed by the recycle compressors and routed to the reaction section - a liquid phase including the products of the process water reaction. The process water is separated and treated The resulting liquid is expanded before being routed to the MP separator. The gas phase in the separator contains H2, H2S and light hydrocarbons and is routed to the HP amine washing installation. The liquid phase is reheated to the required temperature and fed to the fractionation section.

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2005 ENSPM Formation Industrie - IFP Training

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4-

DISTILLATION SECTION
The section includes: - a debutaniser that separates C4 gases from gasoline and heavier fractions - a depropaniser that produces a C1 - C2 - C3 - H2S - NH3 gas fraction for amine washing, and a butane fraction - an atmospheric distillation column that separates light gasoline, heavy gasoline and kerosene fractions - a vacuum distillation column that separates the gas oil fraction from the recycle

5-

HYDROCRACKING CATALYST ACTIVATION

Hydrocracking catalysts are manufactured as oxides (usually by metals salts impregnation on a support, followed by calcination) and need to be sulfided before use. Sulfidation: - MoO 3 + 2 H2S + H2 MoS2 + 3 H2O - 3 NiO + 2 H2S + H2 Ni3S2 + 3 H2O Sulfiding methods Under H2 pressure, with a sulfiding agent added in gas phase, or more frequently in the liquid, which decomposes into H2S and hydrocarbons. Dimethyl disulfide DMDS CH3 S S CH3 + 3 H2 Passivation The cracking function of the zeolite is very active and has to be passivated to avoid early coking of the catalyst, this is done by an injection of aniline. The aniline breaks in NH 3 which temporarily neutralizes the active sites of the catalyst. The catalyst activity is then restored by a temperature increase which desorbs NH 3 . 200C 2 H2 S + 2 CH4

6-

CATALYST REGENERATION
The deactivation is the result of coke deposition. The activity is recovered by burning the coke. It is done either in-situ or ex-situ after catalyst unloading under inert atmosphere. However metals contamination is irreversible. Regeneration consists in a controlled coke burn off. Sulfides are also converted back to oxides.

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2005 ENSPM Formation Industrie - IFP Training

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Reactions Mo S2 Ni 3 S 2 C H2 + + + + 7 O 2 2 7 O 2 2 O2 1 O 2 2 Mo O3 + 2 SO2 3 Ni O + 2 SO2 CO 2 H2O

In-situ method shutdown unit nitrogen purge combustion of coke presulfiding

Ex-situ method The used catalyst is pyrophoric and the contact with air should be avoided. The catalyst should be unloaded under nitrogen in drums and sent to an outside company for regeneration.

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2005 ENSPM Formation Industrie - IFP Training

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IV - HYDROGEN PRODUCTION 1PRINCIPLE OF THE REACTION

The hydrogen required by a hydrocracking unit comes chiefly from the hydrogen atoms linked to the carbon atoms in the light hydrocarbon molecules constituting the feed of a hydrogen production plant. The thermal breakdown of hydrocarbons produces hydrogen gas. Thus methane, for example, gives the following result: CH4 thermal breakdown C solid + 2 H2

Hydrogen production is automatically accompanied by solid carbon deposition which makes the process unusable. The carbon deposit can be eliminated by operating in the presence of steam. At high temperature the water reacts chemically on the solid carbon and forms two gaseous products, carbon monoxide and hydrogen. C solid + H 2O CO + 3H 2

The breakdown of methane in the presence of steam leads to the following reaction: CH4 + H 2O CO + 3H 2

The hydrogen so formed comes partly from the methane and partly from the water which is chemically broken down by the reaction. The process based on this principle is called STEAM REFORMING. The reaction involved in reforming is extremely endothermic (60 kcal consumed per mole of methane converted). It is promoted by high temperatures and the operating temperature is generally around 800C. It also requires moderate pressure of around 20 bar, a substantial amount of excess steam (about 3 tons of steam per ton of hydrocarbon feed) and a specific catalyst (Nickel on Alumina) to direct the conversion process toward maximum hydrogen production and to limit carbon deposition. In addition to the steam reforming reaction, the carbon monoxide formed may react on the excess steam, producing supplementary hydrogen gas: CO + H 2O CO 2 + H2

This conversion is called the CO CONVERSION reaction or SHIFT reaction. Unlike the reforming reaction, CO conversion is exothermic (10 kcal per mole of CO converted). High temperatures have a negative effect on the reaction and a high rate of conversion is obtained only with a moderate temperature. The reaction also requires a specific catalyst (Iron or Chromium). As can be seen, hydrogen production consequently has to be divided into two successive chemical stages : - first, the steam reforming reaction that takes place at high temperature - second, supplementary hydrogen production by CO conversion, carried out at low temperature after cooling the reformer effluent.

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2005 ENSPM Formation Industrie - IFP Training

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2-

HYDROGEN PRODUCTION PLANT

The principle of the hydrogen production plant is shown in Figure 3 and the plant in Figure 4. A number of important operations are involved. a - Preparation of the feed The catalysts used in the hydrogen plant are very sensitive to some POISONS, mainly SULFUR and CHLORINE. The light hydrocarbons used as feed for the unit: - CATALYTIC REFORMING PURGE gas - HP and LP FUEL GAS after AMINE WASHING - commercial BUTANE must therefore be carefully purified. The purge gas from the catalytic reformer contains traces of hydrochloric gas (HCl) and is dechlorinated on beds of specific ADSORBENT (caustic soda). After compression and reheating to the required temperature, intensive desulfurisation of the feed is performed by conventional CATALYTIC HYDROTREATMENT in a reactor containing a catalyst consisting of cobalt molybdenum on an alumina support. The H2S generated by the desulfurization reactions is chemically trapped by the ZINC oxide contact mass. b - Steam reformer furnace The purified feed, combined with the superheated MP steam (approximately 3 tons of steam per ton of feed) is routed to the reformer furnace. The reforming reaction requires substantial addition of very high temperature heat, which calls for original technology. The feed mixture is distributed evenly in a large number of tubes 10 m long and placed vertically in the radiation chamber of the reformer furnace. The feed circulates from top to bottom of the tubes heated by the radiation of the burner flames and on its way it contacts the catalyst which is present inside the tubes in the form of small rings about 1 cm in size. NICKEL, on an inert alumina support, is the active substance of the catalyst. It also contains POTASSIUM which activates breakdown of the water and thereby limits carbon deposition. Operating pressure is in the region of 20 bar and temperature is around 800C. A significant amount of heat is recovered from the very hot flue gases leaving the radiation zone of the furnace. It is used to generate HP and MP steam, to preheat the feed and the furnace combustion air. c - CO conversion The effluent leaving the furnace contains a large amount of hydrogen (70 - 80% volume excluding steam), a small amount of carbon dioxide and non-converted methane, and a non-negligible amount of carbon monoxide (generally over 10% volume). After cooling to around 350C by heat exchange in a steam generator, the CO conversion reaction takes place. The converter reactor contains a fixed bed of iron and chromium based catalyst. The carbon monoxide is partially converted by the steam into hydrogen. The reaction is exothermic and the temperature rises as the effluent passes through the catalyst bed. At the converter outlet the gaseous effluent is hydrogen enriched and its carbon monoxide content has been drastically reduced (to about 1% volume on dry gas).

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2005 ENSPM Formation Industrie - IFP Training

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d - Hydrogen purification The converter effluent is cooled and the dilution water is condensed. The final hydrogen purification is performed by adsorption. The hydrogen passes through a fixed adsorbent bed and the impurities are fixed on the adsorbent. Once it is saturated the adsorbent has to be regenerated. The normal regeneration method is to raise the temperature of the bed by circulating a hot gas through it which desorbs the impurities. The bed then has to be recooled before it can be used again for adsorption. Although this method of desorption by temperature variation, known as thermal swing adsorption (TSA) is very effective, it nevertheless has a disadvantage. The heating and cooling phases are time consuming and consequently it cannot be applied to frequent cycle operation. It also possible to regenerate adsorbent beds at ambient temperature by reducing the operating pressure. This method is known as pressure swing adsorption (PSA). Its advantage is that it is very fast and therefore lends itself to operation by cycles in close succession, thus making it possible to process large quantities of gas effluent with a high impurity content.

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2005 ENSPM Formation Industrie - IFP Training

"SERIES FLOW" HYDROCRACKER Simplified flow scheme

Figure 1
60 RECYCLE COMPRESSOR M Process water 3.5 AUXILIARY COMPRESSOR + NH3 + H2S HP SEPARATOR quench LP SEPARATOR vacuum FURNACE 420 20 GAS SEPARATION C4 DEBUTANIZER

FRESH HYDROGEN

HYDROTREATMENT REACTOR 380

CONVERSION REACTOR

360

185 170

GAS PROPANE BUTANE

quench

FURNACE

420

LIGHT GASOLINE HEAVY GASOLINE KEROSENE

FEED VACUUM DISTILLATE Recycle

125

VACUUM COLUMN

Vacuum distillate

C 5+

ATMOSPHERIC COLUMN
D PCD 315 B

GASOIL

2003 ENSPM Formation Industrie

POSSIBILITIES OF SOLID NH4HS FORMATION

Figure 2

From H2S and NH3 gas as a function of temperature H2S and NH3 partial pressures of the gas For any temperature t

Partial pressure H2S

Possible formation of solide NH4 HS NH3 (g) + H2S (g) No solid NH4 HS NH4HS (s)

Partial pressure NH3

0.1 10 9 8 7 6 5 4 3 0.2 0.3 0.4 0.5 0.6 0.7 0.80.9 1 2 3 4 5 6 7 8 9 10 10 9 8 7 6 5 4 3

Partial pressure H2S (bar)

Te

mp

era

tur

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3

40
35

e4

5 C

30
25 C

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3

20

0.2

15
10 C

0.2

0.1 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.80.9 1 2 3 4 5 6

Partial pressure NH3(bar)

2003 ENSPM Formation Industrie

D PCD 908 B

0.1 7 8 9 10

PRINCIPE OF HYDROGEN PRODUCTION PROCESS

Figure 3

HYDROGEN FROM CATALYTIC REFORMER

MP AND FUEL GAS FROM AMINE WASH

BUTANE

HCI REMOVAL

VAPORISATION

Hydrogen from PSA

HYDRODESULFURATION

340 24

H2S REMOVAL MP STEAM STEAM REFORMING H2 CH4 CO2 CO + H20 % Vol. 73.3 6.0 9.7 11.0 100.0 800 23 CO CONVERSION t C P bar

340 22

CONDENSATE RECOVERY % Vol. 78.9 H2 CH4 5.2 CO2 14.5 CO 1.4 + traces H20 100.0 % Vol. 99.99 traces 20ppm 100.0 TO HYDROCRACKER

PSA PURIFICATION

CONDENSED WATER H2 CH4 CO2 CO

2003 ENSPM Formation Industrie

D PCD 2002 B

H2 CH4 CO2 CO

% Vol. 29.0 17.5 46.0 7.5 100.0

PURGE GAS TO FUEL

Vaporiser FG 44 tubes per row 11burners per row Figure 4 FG

LIQUID BUTANE

E 01

MP steam

HYDROGEN UNIT

FG

A-B-C Steam E 02 Steam water water

H2 from PSA

K01

E 03 F 01 R 02

Gas from PSA

HP FG

HP FG E 04

B 01

EA 01

REFORMER FURNACE MP GENERATOR Water and steam RAW H2 to PSA

To PSA

H2 from CATALYTIC REFORMER R 03 A R 03 B

Hydro desulfurisation REACTOR

R 01 B

E 05 08

EA 02

R 04

B 04

Preheater

B 05

R 01 A To PSA H2S ABSORBERS Pressures (bar) Flowrate (t/h) CO CONVERTER

HCI ABSORBERS

Condensates

2003 ENSPM Formation Industrie

D PCD 1175 A

Temperatures (c)

HYDROGEN PRODUCTION UNIT - STEAM REFORMING Flow scheme

Figure 5

STEAM (3 t/t) CH 4 % 6 79 14 1 100

FEED SULFUR - FREE LIGHT HYDROCARBONS

STEAM REFORMING FURNACE
H2 CO 2 CO

CH 4

100%

Fuel

Stack gases

25 bar

800C

CATALYTIC CONVERSION OF RESIDUAL CO 340C 20 bar

HYDROGEN PURIFICATION (PSA)

HYDROGEN 99.9%

Catalyst tubes CO CO2 CH 4

Steam reforming reaction CH4 + H2O CO + 3 H2

% 6 CH 4 H2 CO 2 CO 73 10 11 100

CO conversion reaction CO + H2O CO2 + H2

2003 ENSPM Formation Industrie

D PCD 316 B

CO conversion reaction CO + H2O CO2 + H2

HYDROGEN PRODUCTION UNIT - PARTIAL OXIDATION (POX) Process flow scheme

Figure 6

OXYGEN
HP regulating steam
13.1

32.5

i.e. 60,000 Nm3/h Steam HP

BURNERS (X2)

28.6

5.7 40

FEEDS
68 70

HYDROGEN 99.5%
66

WATER WASHING OF GASES

1300 1450

Visbroken vacuum residue bitumen sp.gr.15 = 1.169 4 6% wt sulfur Ni + V = 800 ppm weight
Water Water CO2 H2 S to CLAUS unit

Feed + Carbon

CONVERSION OF CO CO + H2O CO2 + H2

P S A

Purge to fuel gas

ELIMINATION H2S and CO2

Separation carbon-ash

Ash + metals
Water

From "Petroles et Techniques" - Sept. - Oct. 1994 (Texaco Process)

2003 ENSPM Formation Industrie

D PCD 317 B

To waste water treatment