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The chemistry of catalytic reforming

The chemistry of catalytic reforming

Catalytic reforming is a complicated process which involves various transformations of hydrocarbons. Straight run gasoline fractions, which are the raw material of the catalytic reforming, contain parafins, naphthenes and aromatics.

The reactions in the catalytic reformers deeply transform the hydrocarbons. Aromatization of hydrocarbons is the main and most important direction of the process. Before looking at various reactions, it should be noted that reforming catalysts feature two types of catalytically active centers: dehydrating centers on platinum and isomerizing centers on the carrier.

One of the main reactions of the process is dehydration (dehydrogenation) of naphthenic hydrocarbons. Dehydration of pentatomic hydrocarbon rings of naphthenic hydrocarbons occurs through formation of cycloolefine hydrocarbons with rearrangement of the ring.

The second type of reaction is dehydrocyclization of paraffinic hydrocarbons; the mechanism of this reaction is not entirely clear yet. Aromatization of paraffinic hydrocarbons may occur either by formation of naphthenic or olefinic and cycloolefinic hydrocarbons.

Other main reactions of the process include isomerization of paraffinic hydrocarbons, which occurs via an intermediate stage of carbonium ion formation; in reforming conditions isomerization leads to formation of unbranched isomers.

Hydrocracking reactions run in parallel on reforming catalysts.

Hydrocracking affects paraffinic hydrocarbons, and, to a lesser extent, naphthenic hydrocarbons. Hydrocracking of paraffins occurs in several stages through formation and disintegration of carbonium ions. Propane and high-molecular compounds prevail in the products of this reaction. Hydrocracking occurs on acidic centers of the catalyst, but the first and final stages of the process, I.e. formation of olefins and hydration of other breakdown products, occur on the metal parts of the catalyst, which feature the hydration-dehydration function.

Hydrocracking of paraffinic hydrocarbons leads to formation of two or more hydrocarbons with lower molecular mass.

In some cases of reforming, hydrogenolysis becomes significantly developed on the metal parts of the catalyst. Unlike hydrocracking, hydrogenolysis leads to more prominent formation of gaseous hydrocarbons, especially methane. In the process of hydrogenolysis, the destruction of carbon-carbon bonds of methyl cyclopentane leads to formation of paraffinic hydrocarbons.

Besides, reforming favors reactions which significantly influence catalyst activity and stability; including formation of coke on the catalyst, as well as hydrodecay of sulfuric, nitric and chlorine substances.

Formation of coke is related to the reactions of compaction on the surface of the catalyst. This causes not only reduction of catalyst activity, but also degrades process selectiveness. Coke formation is promoted by decreased partial pressure of hydrogen and molar hydrogen/raw material ratio, poisoning of the catalyst by contact poisons, disruption of balance between hydrating and acidic functions of the catalyst, processing of raw material with increase content of light (C5 – C6) and heavy (C10 and above) hydrocarbons.

The fastest of the main reforming reactions is the reaction of dehydrogenating of alkyl cyclohexanes into the corresponding aromatic hydrocarbons, the slowest reactions are de dehydrocyclization of paraffinic hydrocarbons. The rate of naphthenic and paraffinic C6 – C10 hydrocarbons increase on homologous sequences with the increase of molecular mass.

Reforming reactions leading to formation of aromatic hydrocarbons from naphthenic and paraffinic substances absorb heat; hydrocracking and hydrogenolysis reactions emit heat, isomerization reactions of paraffinic and naphthenic hydrocarbons have little thermal effect. For C5 – C10 hydrocarbons, molar thermal effects are almost independent of molecular mass and change little in the temperature range of 470 – 500oC.

Hydrotreatment catalysts

A catalyst for hydrotreatment must be highly selective: reactions of C-C bond breaking or saturation of aromatic rings must practically not occur in its presence. It must be highly active in breaking С-S, С-N, С-О bonds and adequately active in reactions of saturation of unsaturated compounds (which form with light destruction or are already present in the raw material, if it is a mix with secondary process products). In the processes of hydrotreatment of various oil fractions and products, any sulfur resistant hydrating catalyst can be used, e.g. combinations of oxides and sulfides of cobalt (or nickel) with oxides or sulfides of molybdenum or tungsten, specifically cobalt (or nickel) molybdate, nickel sulfo tungstates etc.

Some of the catalysts which comply with these requirements are alumina-cobalt-molybdenum (ACM) and alumina-nickel-molybdenum (ANM). In some cases, alumina-nickel-molybdenum silicate (ANMS) is also used.

 

Hydrotreatment catalysts

Weight content, % of active components,

minimum

ACM

ANM

ANMS

СоО

NiО

МоО3

SiO2

Max impurities

Fe2О3

Na2O

Strength Index on the chopping kg/m

4.0

12.0

0.16

0.08

1.1

4.0

12.0

0.16

0.08

1.0

4.0

12.0

5.0-7.0

0.13

0.20

1.2

Catalysts commonly used in the US

Weight content, %

Со-Мо

Ni-Mo

Co-Ni-Mo

Ni-W

СоО

2-3.5

1.25-2.5

NiО

3-5.5

0.35-2.5

5-6

МоО3

9-15

13-18.5

10-11

WО3

19-20

Total oxides

12-18

17-22.5

12.2-15

25

Weight ratio

(СоО+ NiО) МоО3 (WО3)

0.19-0.35

0.21-0.42

0.20-0.32

0.25-0.32

Atomic ratio

(Co+Ni)Mo(W)

0.22-0.41

0.25-0.5

0.24-0.38

0.25-0.32

All the catalysts are very durable mechanically and remain active for a long duration of time. Not only active component content, but also the ratio of metal in the catalyst is important. In ACM catalyst, the most effective ratio of cobalt to molybdenum is 1:5; it ensures maximum activity in hydrodesulfurization reactions. Such catalyst is highly selective and the reactions of C-C bond hydrocracking or saturation of aromatic rings practically do not occur in its presence. Besides, it is very stable to nuclei, which are usually present in the processed material. Moreover, it is sulfided beforehand, and some data indicate that sulfidation ensures good performance of the catalyst in hydrotreatment systems.

This catalyst is adequately active in reactions of unsaturated compound saturation, C-N and C-O bond breaking and is used in practice in hydrotreatment of all oil fractions and products except heavy petroleum residue. The active components of this catalyst are those, which form octahedral oxidic ions, i.e. СоО, СоМоО4 and “complex”. It has been found that the Со2+ ion is distributed evenly between tetrahedral and octahedral forms. Another widely used hydrotreatment catalyst is ANM (alumina-nickel-molybdenum). In terms of activity it is practically identical to ACM when treating distillates, but is preferable when treating raw materials with increase nitrogen compound and polycyclic aromatic hydrocarbon content. Besides, it si about 25% less expensive than ACM and allow 10-200С temperature reduction when hydrotreating light fractions. However, it quickly loses its initial high activity. The ANMS catalyst, due to addition of silica oxide, is stronger mechanically and thermally, and is somewhat better in hydration activity. However, long term influence of steam reduces its mechanical strength (also holds true for ANM).

For hydrotreatment, the temperature, partial pressure of hydrogen and hydrogen sulfide are the determining factors for maintaining the catalyst in sulfide form. It has been determined that the highest activity is demonstrated by molybdenum disulfide and mixed nickel sulfide (NiS and NiS2). The ANM catalyst requires sulfiding, which is not necessary for ACM. A lot of coke, sulfur and metals precipitate on the catalyst in the process: 7 – 20, 0.5 – 1.5 and 12 – 25% of catalyst weight respectively. It loses activity and the degree of desulfurization drops – it is the normal catalyst aging process. The main indication of catalyst aging is increased sulfur content in treated product. Some other factors which accelerate aging of the catalyst are:

  • increased temperature, which decrease yield due to formation of gas and coke. For “fresh” catalyst (especially so for ACM) it is important to determine initial reactor temperature (usually 350-3700С);
  • changing composition of the catalyst. For example, at 7600С the active nickel oxide on alumina oxide transforms into inactive nickel aluminate, sintering of catalyst occurs and active surface decreases;
  • loss of active component; at around 6000С molybdenum trioxide evaporates;
  • insufficient rate of desorption of formed products from the surface of the catalyst at insufficient partial pressure of hydrogen.

The catalyst is quite stable in oxidation or reduction environments up to 550-600 0С, however, long exposure to the same conditions in the presence of steam may lead to decrease of activity and strength. In this case the active surface of alumina oxide decreases and the volatility of the molybdenum oxide increases somewhat. To maintain catalyst activity in the system, first the temperature is raised gradually, and after reaching the allowable temperature maximum, the catalyst is regenerated or replaced with new. Since catalyst activity drops predominantly due to coke precipitation into its pores, the process of regeneration involves burning the coke. This process requires the hydrotreatment system to be switched to catalyst regeneration mode.

Particle size and catalyst forming is very important in operation of hydrotreatment systems. Of the three types – pelletized, ball and extruded, the latter are considered the best. No more than 5% of the catalyst used today are pelletized.

Forming method and particle size influence on catalyst performance in hydrotreatment.

Catalyst

Grain size,

mm

Equivalent diameter, mm

System pressure drop, kPa

Relative activity.

pelletized

4.8

4.76

107

1.00

extruded

3.2

3.66

109

1.16

pelletized

3.2

3.18

111

1.24

extruded

1.6

2.13

117

1.58

ball

1.5

1.59

123

1.82

The information above demonstrates feasibility of using extruded catalysts in hydrotreatment. The advantages are especially evident when treating heavy distillates, since catalyst activity is higher than that of pelletized.

Additive treatment and salt removal

HFO is a very chemically complex mix of high molecular organic, heteroorganic and metal-organic compounds. Structurally, HFO is a multi phase dispersed system. The dispersed phase particles include paraffin hydrocarbons, carbenes and carboids, solid mineral particles, water globules, gas bubbles etc. Settling of dispersed particles and formation of solid sediment complicates all stages of transportation, storage and burning of HFO. Carboids and minerals are abrasive to pumps, valves and nozzles. Water globules complicates operation of HFO facility, negatively impacts combustion and may lead to flameout. Presence of harmful substances in HFO generates derivatives, corrosion and contamination and reduces heat efficiency. To reduce the negative impacts of usin HFO, it must be specially treated at an oil refinery or immediately before burning. There are three methods of treatment: hydromechanical, physical and chemical.

Hydromechanical treatment is done in special systems (rotary, jet, vibrational etc), which allow to create a fine mix of HFO with viscous sediment and water. The HM method is useful when burning cracking HFO or HFO with high water content. As a result of the treatment, water and HFO mix to microemulsion. As water boiling temperature is significantly lower that  of HFO (280…320°С), when HFO enters the combustion chamber, the emulsified water evaporates, which leads to microexplosions of HFO droplets and further atomization. The flame is distributed more evenly, combustion is accelerated and becomes more complete, temperature range is more uniform, temperature maximum in the combustion area is reduced, therefore emission of thermal nitrogen oxides is reduced by 30-40%. The amount of emulsified water in HFO is recommended at 6 – 12% with droplet size 10 – 15 micron.

Physical methods include processing of fuel with magnetic, electric, thermal and other physical fields to increase its dispersion, stability, and, ultimately, improve combustion.

Salts removal involves water rinsing of HFO. Fresh water is injected into the HFO, water-fuel emulsion is created, then the rinsing water saturated with salts (mostly of alkali metals) is removed by centrifuges. Abroad (Pegrolant company in the USA) water is removed from HFO electrostatically directly in fuel tanks.

The chemical method involves various additives. There are a number of additives serving different purposes.

Depressors improve flow. Copolymers of ethylene and vinylacetate are used as depressants.

Dispersion additives prevent formation of tar sediment, increase combustion rate. Dispersion and anti-smoke additives are compounds of Mn, Be, Cr etc (combustion catalysts), compounds of Ba and Ca, alumina silicates. The latter accelerate thermooxidation cracking of the fuel, which positively affects combustion, reduces corrisive activity of smoke gases; alumina silicates are not yet used in energy production.

Anticorrosive additives are compounds of Mn, Al, Bl, Be etc. They react with corrosion and adhesive components of combustion products and render them inert. The outside of the boiler becomes covered with soft easily removed sediment, metal corrosion rate reduces drastically.

The additive, coming to the power plant, is unloaded into special tanks, where actual operating solution is prepared. The solution is then directed to special storage tanks for liquid additive. From these tanks, a portioner pumps the liquid through filters to second stage HFO pumps (with ejection type blenders).

Some of the widely used additives are based on Mg, Mn and Al dispersed in oil.

 

Pressurizing the fuel before combustion

Pressure of liquid fuel is selected based on the required dispersal of the fuel for a given nozzle efficiency. Pressure of HFO before the nozzles is chosen based on the required nozzle power. Fuel pressure before the nozzles can be low (less than 0.7 MPa), medium (less than 3.5 MPa) and high (over 3.5MPa). The required pressure is reached by using pumps of various types and purposes.

Gear pumps are used to pump HFO colder than 80°С and are used as circulation and main pumps in industrial boilers; feed from 0.22 to 9m/hour, pressure 0.6 to 2.5MPa.

Screw pumps (three screws) are used to pump HFO colder than 100°С at various HFO facilities or industrial boilers as main pumps; feed 0.45 to 6.84 m3/hour, pressure 2.5 to 4 MPa.

Centrifugal pumps are designed for pumping of HFO colder than 80°С and are used at thermal power plants as main pumps and first raise pumps, feed 35 to 560 m3/hour, pressure 0.7 to 3.7 MPa.

Heating HFO before nozzles

Before injecting liquid fuel into the boiler, it is heated for proper viscosity. The temperature of heating is defined by type of HFO and atomization method (see table1).

Table 1

HFO heating temperature before nozzles, °С

HFO type

Mechanical nozzles

Steam mechanical nozzles

Rotary and steam atomization nozzles

100

150 (135)

125

100

100 В

125

115

40

120

110

90

40 В

110

100

F

80

80

 

Steam goes to HFO heaters (Fig 2, pos 7) from turbine bleed or directly from the boiler at 1.6Mpa at up to 300°С (saturated or somewhat overheated).

Figure 5 shows the design of a double pipe heater, used in HFO facilities.

Fig. 1.5. Double pipe HFO heater.

 

Atomization of liquid fuel and creation of fuel-air mixture.

These stages are critical in fuel preparation for combustion. Quality of atomization and mixture creation directly influences economy and reliability and the combustion process in various modes of operation. Atomization of liquid fuel is done in nozzles, fuel and air mixture is created in burners of various types and designs.

The main nozzle types used in energy production are mechanical and nozzles with atomization media. Mechanical atomization involves pushing the fuel through a small orifice (1…3 mm) at significant pressure (1.0…2.0 MPa). The atomizing part of a centrifugal nozzle (head) is shown in Figure 6. It consists of three main components. In the disk 4, the fuel is separated into small streams, in the disk 5 the stream vortices are created, and the fuel is atomized in the nozzle inset 6.

 

Figure 6. Mechanical nozzle head: 1 – head inset; 2 – stop nut; 3 – covering nut; 4 – distribution disk; 5 – vortex disk; 6 – nozzle inset.

 

Steam or air kinetic energy cause atomization in steam or pneumatic nozzles. E.g. in stream nozzles as shown in Figure 7, HFO is atomized by direct influence by steam kinetic energy and ejection.

Figure 7. Stream nozzle: 1 – plug; 2 – gasket; 3 – atomizer; 4 – steam collector; 5 – body; 6 – fuel shaft; 7 – steam shaft.

 

Steam and pneumatic/mechanical nozzles atomize fuel by simultaneous influence of both mechanical and stream (pneumatic) swirlers. Such nozzles are double-shaft (atomization agent influences the fuel when the fuel exits the nozzle into the furnace (Fig.8) or double-shamber (streams of fuel and atomization agent interact inside the nozzle) with one outlet.

Figure 8. Steam/mechanical nozzle head: 1 – covering nut; 2 – distribution washer; 3 – fuel swirler; 4 – steam swirler.

 

In rotary nozzles fuel is atomized and ejected into the furnace by rotating cylinder (Figure 9). The fuel enters the nozzle through hollow pipe, then to the wall of the cylinder, where it is distributed as film, which cuts off at the cylinder’s edge. Additional air (10…20% of combustion air) is fed to the glass to further influence the fuel film. The rich mixture of air and fuel drops enters the furnace.

Combustion efficiency depends on atomization quality, which is characterized by the droplet size distribution, mean droplet diameter, spray angle, stream range and stream concentration, i.e. the amount of liquid passing through a unit of stream cross-section area in a unit of time.

Fractional constitution of drops in the stream may be presented as a normal Gaussian distribution dependency.

Figure 9. Rotary nozzle head: 1- fuel feed pipe; 2- hollow rotating shaft; 3 – body; 4 – feeder; 5 – rotating atomization cylinder; 6 – air swirler.

Figure 10. Drop distribution frequency curve.

Graphical representation is shown in Figure 10. The curve demonstrates that drop size distribution is quite uneven.