ACID REGENERATION ALKYLATION SPENT ACID

FEBRUARY 2002 FROM: SULPHURIC ACID TECHNOLOGY 1. Introduction Alkylation of isobutane with C3-C5 olefins is generally considered to be the best method of producing high octane number gasolines for motor vehicles. The classic reaction involves isobutylene and isobutane to produce trimethyl pentane (isooctane), which has a defined octane number of 100. CH3 | CH3-C=CH2 CH3 | CH3-CH-CH3 CH3 The above reaction is a catalyst based reaction that has been used throughout the world since the phaseout of lead based octane gasoline additives. Concentrated sulphuric acid in the range of 88% to 92.5% H2SO4 is used as a catalyst for the reaction with approximately an equal amount of water and organics making up the remaining portion. In theory, a catalyst promotes a chemical reaction and is not consumed or modified by the reaction. In the alkylation reaction, the acid is diluted as a result of side reactions and feed contaminants. The alkylation process consumes approximately 0.18 to 0.27 kgs (0.4 to 0.6 lbs) per gallon of alkylate. The loss of sulphuric acid is made up by fresh concentrated (98.5 wt%) sulphuric acid and a bleed stream of spent acid is removed from the process. The spent acid stream undergoes a series of process steps to remove entrained hydrocarbons which are returned to the process with the spent acid being sent to storage. The acid concentration in the alkylation process must be strictly controlled to prevent runaway reactions from occurring. A runaway reaction will occur when the acid strength is between 85 to 87% H2SO4. At the acid concentration, the reaction conditions do not favour the alkylation reaction between olefins and isobutane. Instead, olefins will react with each other to form conjunct polymers which are also known as acid sludge, acid soluble oil and read oil. The conjunct polymers are soluble in sulphuric acid which has the effect of decreasing the concentration of the sulphuric acid. As the acid concentration decreases, the reaction to form additional conjunct polymers is favoured and the reaction accelerates. Another reaction that occurs is the oxidation of polymers by sulphuric acid. The polymer is oxidized to a tar like substance and sulphuric acid is reduced to water and SO2. These reactions can occur within the alkylation process unit or in the spent acid storage tanks. The acid regeneration or spent acid recovery process is designed to regenerate or recover sulphuric acid from a variety of spent acids containing a varying degree of contaminants. CH3 | --> CH3 | CH3-C-CH2-CH-CH3 |

A typical sulphuric acid regeneration plant consists of three major components: 1. 2. 3. Regeneration furnace for the decomposition of spent acid Gas cleaning system Contact sulphuric acid plant

The basic process is the decomposition of H2SO2 in a furnace operating at 1000 to 1200C. The decomposition reaction is an endothermic reaction so heat must be provided for the reaction to occur. Hydrocarbons that are present in the spent acid provide part of the fuel to maintain furnace operating temperature with the remaining portion being supplied by burning fuel such as natural gas, No. 2 fuel oil, etc. 2. Regeneration Furnace A regeneration furnace is generally a horizontal refractory lined furnace designed to decompose H2SO2 into SO2 and H2O. The key design parameter is the residence time which should be sufficient to allow the decomposition reaction to go to completion. Typically, a three (3) second residence time is provided. Spent acid is typically spray into the furnace at one end using a two-fluid atomizing type spray nozzle with compressed air as the atomizing fluid. At the same end of the furnace, fuel burners provide the additional heat input to maintain the decomposition reaction and furnace operating temperature. Sulphur can also be burned in the regeneration furnace to supplement acid production. Sulphur burned in the furnace will reduce the quantity of fuel required since it is an exothermic reaction. Combustion air required for the process can be enriched with oxygen to varying degrees all the way to 100% oxygen. The use of oxygen enrichment reduces the amount of gaseous inerts (i.e. nitrogen) that must be carried through the downstream equipment. In an existing plant this has the effect of increasing the throughput of spent acid without the need to increase the size of downstream equipment. In a new plant the overall size of equipment can be reduced. The use of oxygen enrichment also increases the SO2 concentration providing for a smaller downstream sulphuric acid plant. Regeneration furnaces are typically operated with a 2% oxygen content in the gas exit the furnace. The hot gases leaving the furnace enter a waste heat boiler where high pressure steam is generated for process use or power generation. The gases are cooled to about 350-375C before entering the gas cleaning section of the plant. 3. Preconcentration Preconcentration of the waste acid feed reduces the amount of water that must be handle in the furnace. The result is a reduction in the size of furnace and the amount of fuel burned. The degree to which the feed can be concentrated is dependent on the concentration of solubles in the waste acid. The waste acid can be concentrated to the point where these solubles begin to precipitate out of solution.

4. NOx NOx is a general term used to describe nitrogen oxide (NO) and/or nitrogen dioxide (NO 2). NOx is generally classified as either fuel NOx or thermal NOx depending on how it is formed. Fuel NOx results from the oxidation of fuel bound nitrogen while thermal NOx is created by the fixation of nitrogen in the combustion air at high temperatures. The formation of fuel NOx is dependent on the nitrogen content of the fuel, total excess air/oxygen and relative distribution of primary and secondary combustion air/oxygen. Formation of thermal NOx is affected by the oxygen concentration, temperature, pressure and residence time. Some general parameters regarding the formation of thermal NOx are:

Thermal NOx production rate doubles for every 90 K temperature increase beyond 2200 K (1927C, 3500F) Above 1538C (2800F) significant quantities of thermal NOx is generated Thermal NOx increases exponentially (~ 4th power) with absolute temperature Thermal NOx increases roughly with the square of the available oxygen

Corrosion
June 6, 2005

Introduction The moment process gases or liquids are introduced to the plant, corrosion begins and the plant starts its slow but sometimes fast decline. Selecting the correct materials of construction is the best method of slowing the progress of corrosion. In order to select the correct material the designer and operator of an acid plant must know how a particular material will withstand exposure to the process conditions. Back to top Carbon Steel Although the overall corrosion rate of carbon steel in concentrated sulfuric acid service is low, some corrosion still occurs. The reaction products from the corrosion process are iron sulfate and hydrogen gas.
Fe + H2SO4 -> FeSO4 + H2

This reaction can be considered as the sum of two different reactions occurring at different sites on the metal surface: Fe -> Fe++ + 2e- (oxidation) 2H+ + 2e- -> H2 (reduction) The iron sulphate film is relatively weak and can be disturbed by high acid velocities or other disturbances in the liquid.

Hydrogen gas can be a problem with carbon steel in sulphuric acid environments because it can literally scrub off the mechanically weak iron sulphate film, which is the only thing protecting the steel from attack. During periods of normal flow, the gas bubbles are very small and evenly distributed, and they are quickly carried downstream along with the acid, generally without causing a problem to the pipe wall. However, when acid flow stops, the gas bubbles accumulated along the pipe wall in the upper half of the pipe. When the flow resumed, the hydrogen gas bubbles are dislodged and rise to the very top of the pipe, scrubbing off the protective film along the way. With the film gone along the top of the pipe, the surface corroded very quickly until the iron sulphate film reforms. Repeating this process over and over again results in a pattern of curved grooves in the top half of the pipe, all radiating toward a central longitudinal groove at the very top. Although we're usually not privileged to see such an excellent example of hydrogen grooving, it's not an uncommon occurrence in sulfuric acid service, particularly under upset conditions. To guard against it, the usual recommendation is to use very thick steel, in recognition of the possibility of localized corrosion, and to keep the average velocity in pipes below 3 ft/sec to reduce the scrubbing effect of any hydrogen bubbles that do form. Back to top Corrosion Charts Corrosion charts are one source of information that will help identify the correct material of construction for a particular application. Material Description Isocorrosion Curves Corrosion Rate = 0.1 mm/y (4 mpy) 0-50% H2SO4, 2000 ppm Chloride Ions, Corrosion Rate = 0.1 mm/y (4 mpy) Naturally Aerated, Corrosion Rate = 0.1 mm/y (4 mpy) 0-100% H2SO4, 2000 ppm Chloride Ions, Corrosion Rate = 0.1 mm/y (4 mpy) 0-100% H2SO4, 200 ppm Chloride Ions, Corrosion Rate = 0.1 mm/y (4 mpy) Isocorrosion Curves 0-100% H2SO4
Type 310M Corrosion Rates in Strong Sulphuric Acid

Source

654 SMo UNS S32654, Avesta Bulletin 9603 Avesta Sheffield Corrosion Handbook, Avesta Sheffield, 1994

254 SMo

300 Series Stainless Steels 310M Stainless Steel

? ?

654 SMo UNS S32654

Isocorrosion Curves Corrosion Rate = 0.1 mm/y (4 mpy) 0-50% H2SO4, 2000 ppm Chloride Ions, Corrosion Rate = 0.1 mm/y (4 mpy) Naturally Aerated, Corrosion Rate = 0.1 mm/y (4 mpy) 0-100% H2SO4, 2000 ppm Chloride Ions, Corrosion Rate = 0.1 mm/y (4 mpy)

654 SMo UNS S32654, Avesta Bulletin 9603 Avesta Sheffield Corrosion Handbook, Avesta Sheffield, 1994

904L

Isocorrosion Curves Corrosion Rate = 0.1 mm/y (4 mpy) 0-50% H2SO4, 2000 ppm Chloride Ions, Corrosion Rate = 0.1 mm/y (4 mpy) Naturally Aerated, Corrosion Rate = 0.1 mm/y (4 mpy) 0-100% H2SO4, 2000 ppm Chloride Ions, Corrosion Rate = 0.1 mm/y (4 mpy) 0-100% H2SO4, 200 ppm Chloride Ions, Corrosion Rate = 0.1 mm/y (4 mpy) Corrosion Rate Corrosion Rate Isocorrosion Curves Corrosion Rate in Non-Aerated H2SO4 at 80C (176F) Corrosion Rate versus Concentration in Boiling H2SO4, 0-50% H2SO4 Isocorrosion Curves 0-100% H2SO4 Corrosion of Annealed 20Cb-3 to Boiling H2SO4 at Various Concentrations (5%, 10% and 25% H2SO4) Isocorrosion Curves Isocorrosion Curves Isocorrosion Curves Corrosion Rate = 20 mpy Isocorrosion Curves Corrosion in Sulphuric Acid Corrosion Rate = 20 mpy

654 SMo UNS S32654, Avesta Bulletin 9603 Avesta Sheffield Corrosion Handbook, Avesta Sheffield, 1994

Alloy C-22 Alloy G-30 Carbon Steel

? ? ?

Carpenter 20Cb-3

20Cb-3 Stainless Steel, Carpenter Technology Brochure

Chlorimet 2 Chlorimet 3 Durimet 100

The Duriron Company, Inc., Bulletin A/3g, April 1987 The Duriron Company, Inc., Bulletin A/3g, April 1987

Durimet 20

Durimet 20, Bulletin A/1h, The Duriron Company, Inc., January 1985 Durimet 100, Bulletin A/7g, The Duriron Company, Inc., July 1987 Duriron, Duchlor 51, Superchlor, Bulletin A/2g, The Duriron Company, Inc., March 1986 Hastelloy Alloy B-2, Cabot Stellite Division, Brochure, 1977 Hastelloy Alloy C-276, Haynes International, Bulletin H-2002B Alfa Laval Brochure ? ?

Duriron

Isocorrosion Curves Isocorrosion Curves Sulphuric Acid Sulphuric Acid, 200 ppm Chlorides Isocorrosion Curves Sulphuric Acid Sulphuric Acid, 2000 ppm Chlorides Corrosion Rates Reagent Grade Sulphuric Acid at 93C - Corrosion Rates 20-60% H2SO4 Commercial Grade Sulphuric Acid at 130C -

Hastelloy B2

Hastelloy C-276

Hastelloy D-205

Corrosion Rates 96-99% H2SO4 Hastelloy G Corrosion Resistance in Non-Aerated Sulphuric Acid at 80C (176F) General Corrosion Resistance Isocorrosion Curve, 20 mpy (0.51 mm/y) Isocorrosion Curves Isocorrosion Curve Corrosion Rate = 5 mpy Isocorrosion Curve Corrosion Rate = 5 mpy Isocorrosion Curves Aerated, Velocity = 10 m/s, Corrosion Rate = 0.5 mm/y Isocorrosion Curves Deaerated H2SO4, Corrosion Rate = 0.1 mm/y (4 mpy) Corrosion Rate = 0.1 mm/y (4 mpy) Static Conditions, Corrosion Rate = 0.1 mm/y (4 mpy) Isocorrosion Curves Deaerated H2SO4, Corrosion Rate = 0.1 mm/y (4 mpy) 0-20% , Static Conditions, Corrosion Rate = 0.1 mm/y (4 mpy) Isocorrosion Curves Corrosion Rate = 0.1 mm/y (4 mpy) Corrosion Rates - Static Conditions Isocorrosion Curves 80-100% , Static Conditions, Corrosion Rate = 0.1 mm/y (4 mpy) Corrosion Rate = 0.1 mm/y (4 mpy) Isocorrosion Curves Naturally aerated, Corrosion Rate = 0.1 mm/y (4 mpy) Stagnant, Corrosion Rate = 0.1 mm/y (4 mpy) Isocorrosion Curves Deaerated H2SO4, Corrosion Rate = 0.1 mm/y (4 mpy) H2SO4 with Copper Sulphate, Corrosion Rate = 0.1 mm/y (4 mpy) Isocorrosion Curve 1 mpy, 90-100% H2SO4 KSB, Klein, Schanzlin & Becker Aktiengesellschaft, I/1980 Avesta Sheffield Corrosion Handbook, Avesta Sheffield, 1994 Avesta 2205, UNS 31803, Avesta Bulletin 9060 Sandvik Steel, Bulletin S-1875-ENG, July 1992 Avesta Sheffield Corrosion Handbook, Avesta Sheffield, 1994 Avesta SAF 2304, UNS S32304, Avesta Bulletin 9137 Edmeston HT Alloy Brochure Monsanto Enviro-Chem System Brochure Edmeston Materials System Engineering Avesta Sheffield Corrosion Handbook, Avesta Sheffield, 1994 Sandvik Steel, Bulletin S-1875-ENG, July 1992 Carpenter Alloys for Controlling Severe Corrosives, Carpenter Technology Corporation, 9/89-7.5M Magazine advertisement Special Metals Technical Brochure

Inconel Alloy 686

Lead Niobium

Noridur 9.4460

SAF 2205 UNS S31803

SAF 2204 UNS S32304

Sandvik HT 9067

Sandvik SX

Sanicro 28

Titanium

Avesta Sheffield Corrosion Handbook, Avesta Sheffield, 1994

ZeCor

Zeron 100

Isocorrosion Curves Figure 1: Corrosion Rate = 0.1 mm/y (4 mpy) Figure 2: 0-40% H2SO4, Corrosion Rate = 0.1 mm/y (4 mpy) Figure 3: 0-60% H2SO4, 2000 mg/L Cl, Corrosion Rate = 0.1 mm/y (4 mpy) Figure 4: 30-70% H2SO4, Corrosion Rate = 0.1 mm/y (4 mpy) Figure 5: 70-100% H2SO4, Corrosion Rate = 0.1 mm/y (4 mpy) Figure 6: 80-100% H2SO4, Ferrous Ions, Corrosion Rate = 0.1 mm/y (4 mpy) Figure 7: Oleum, 30% SO3, 70-130C Isocorrosion Curve, Corrosion Rate = 5 mpy

The Performance of Zeron 100 Super Duplex Stainless Steels in Sulphuric Acid, Weir Materials & Foundries

Zirconium

Wah Chang Magazine Advertisement

Properties Sulphuric Acid

Introduction Sulphuric acid is a colourless to amber, slightly cloudy, oily liquid with a specific gravity almost twice that of water. At normal temperatures and a concentration of 98% or lower, it has little odour. At higher temperatures and above a concentration of 98% irritating sulphur trioxide (SO 3) fumes may be liberated. Oleum (fuming sulphuric acid) is a colourless to white, heavy, oily liquid containing sulphur trioxide dissolved in sulphuric acid. On exposure to air, oleum releases irritating white fumes of sulphur trioxide. All grades of sulphuric acid have an affinity for water resulting in evolution of heat when diluted. In the case of oleum, the reaction occurs with explosive violence. Sulphuric acid and oleum will absorb moisture from the air resulting in dilution of the acid. All grades are strongly corrosive and personal safety precautions should be carefully followed. Many organic substances, wood, starch, sugar, paper, etc. are charred on contact with sulfuric acid, forming carbon. Very small quantities of organic matter will blacken sulphuric acid as a result of suspended carbon. Clear, colourless liquid Contaminants in the acid may impart a colour to the acid. Sulphuric acid will attack many metals and in its concentrated form is a strong oxidizing agent and may cause ignition on contact with organic materials, nitrates, carbides, chlorates, etc. None

Colour

Reactivity

Flash Point Structure

Specific Gravity Freezing Point Boiling Point Viscosity Conductivity Enthalpy

Varies with concentration and temperature. See Table See Chart See Table See Chart See Table See Chart See Chart See Chart See Chart

Properties
April 12, 2003

Degrees Baum

Specific Gravity (15.6C / 15.6C)

% H2SO4

Freezing Point C F 32 31.2 30.5 C

Boiling Point F 212

0 1 2

1.0000 1.0069 1.0140

0.00 1.02 2.08

0.0 -0.5 -1.0

100

3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37

1.0211 1.0284 1.0357 1.0432 1.0507 1.0584 1.0662 1.0741 1.0821 1.0902 1.0985 1.1069 1.1154 1.1240 1.1328 1.1417 1.1508 1.1600 1.1694 1.1789 1.1885 1.1983 1.2083 1.2185 1.2288 1.2393 1.2500 1.2609 1.2719 1.2832 1.2946 1.3063 1.3182 1.3303 1.3426

3.13 4.21 5.28 6.37 7.45 8.55 9.66 10.77 11.89 13.01 14.13 15.25 16.38 17.53 18.71 19.89 21.07 22.25 23.43 24.61 25.81 27.03 28.28 29.53 30.79 32.05 33.33 34.63 35.93 37.26 38.58 39.92 41.27 42.63 43.99

-1.2 -1.8 -2.1 -2.7 -3.2 -4.0 -4.4 -5.0 -5.6 -6.6 -7.9 -8.7 -9.7 -10.8 -12.2 -13.7 -15.2 -17.0 -18.8 -21.2 -24.0 -27.1 -29.5 -33.5 -37.4 -42.7 -47.8 -54.8 -61.7 -59.0 -57.1 -55.2 -54.1 -53.0 -49.7

29.8 28.9 28.1 27.2 26.3 25.1 24.0 22.8 21.5 20.0 18.1 16.3 14.6 12.6 10.0 7.3 4.7 18.8 -1.8 -6.2 -11.0 -15.4 -21.0 -28.2 -35.3 -44.7 -54.0 -66.6 -79.1 -74.3 -70.8 -67.3 -65.3 -63.3 -57.4 117.8 244 115.6 240 113.3 236 111.1 232 109.4 229 136.1 227

38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 65.5 65.75 65.9 65.92 65.93 65.95 65.97 65.98 66.0

1.3551 1.3679 1.3810 1.3942 1.4078 1.4216 1.4356 1.4500 1.4646 1.4796 1.4948 1.5104 1.5263 1.5426 1.5591 1.5761 1.5934 1.6111 1.6292 1.6477 1.6667 1.6860 1.7059 1.7262 1.7470 1.7683 1.7901 1.8125 1.8239 1.8297 1.8331 1.8335 1.8339 1.8343 1.8347 1.8350 1.8354

45.35 46.72 48.10 49.47 50.87 52.26 53.66 55.07 56.48 57.90 59.32 60.75 62.18 63.66 65.13 66.63 68.13 69.65 71.17 72.75 74.36 75.99 77.67 79.43 81.30 83.34 85.66 88.65 90.60 91.80 92.60 92.70 92.80 92.90 93.00 93.10 93.19

-45.7 -42.5 -38.9 -36.4 -34.1 -32.0 -30.3 -29.2 -28.6 -28.4 -28.8 -29.9 -31.7 -33.1 -36.8 -37.8 -38.8 -42.8 -40.4 -39.6 -34.0 -22.0 -11.2 -2.5 3.9 8.0 7.3 0 -9 -16.5 -23.0 -24.0 -24.8 -25.8 -27.0 -28.2 -29.5

-50.2 -44.5 -38.0 -33.5 -29.3 -25.4 -22.6 -20.6 -19.4 -19.1 -19.9 -21.8 -25.0 -27.5 -34.2 -36.0 -38.0 -45.0 -40.8 -39.2 -29.0 -7.5 11.6 27.5 39.0 46.2 45.2 31.8 16.1 2.3 -9.5 -11.1 -12.6 -14.5 -16.6 -18.8 -21.0

120.0 122.8 126.7 130.6 135.0 139.4 143.9 151.1 158.9 167.8 177.8 185.0 192.2 197.8 207.8 217.2 227.8 247.2 260.0

248 253 260 267 275 283 291 304 318 334 352 365 378 388 406 423 442 477 500

276.1

529

66.01 66.02 66.04 66.1

1.8357 1.8360 1.8364 1.8381 1.8407 1.8427 1.8437 1.8437 1.8424 1.8391

93.30 93.40 93.50 94.00 95.00 96.00 97.00 98.00 99.00 100.00

-29.8 -31.0 -32.1 -32.0 -20.7 -14.7 -6.3 -1.0 4.5 10.0

-21.7 -23.8 -25.8 -25.0 -5.3 5.5 20.7 30.0 40.1 50.7 309.4 589

Boiling Point
September 27, 2003

Associated Links

Freezing Point
September 27, 2003

Viscosity
April 30, 2003