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Chemical synthesisHigh temperatureIndustrial scale

Contact process

Production of sulfuric acid (H₂SO₄) by catalytic oxidation of SO₂ to SO₃ over a vanadium pentoxide catalyst, followed by absorption in concentrated acid. ~270 Mt/year — the world's most-produced acid.

Molecular synthesis through controlled chemical reactions

Key reaction

S + O₂ → SO₂ ; 2 SO₂ + O₂ ⇌ 2 SO₃ ; SO₃ + H₂O → H₂SO₄

Operating conditions

Temperature
400-450°C
Pressure
1-2bar
Catalyst
V₂O₅ / SiO₂ (avec promoteurs K, Na, Cs)
Phase
gas

How it works

Schema coming soon

How it works

Sulfuric acid is the historical indicator of a country's industrialization — its tonnage tracks phosphate fertilizer production, metal refining, organic chemistry and water treatment. The contact process, patented in 1831 by Peregrine Phillips and scaled up by BASF from the 1880s, relies on three steps: sulfur combustion, catalytic oxidation to sulfur trioxide, absorption in concentrated acid. (1) Combustion: elemental sulfur (from natural gas desulfurization or petroleum refining) burns in air at 1000 °C: S + O₂ → SO₂. The gases contain ~10-12 % SO₂. An alternative route — still used in copper/zinc smelters — recovers SO₂ from sulfide-ore roasting gases. (2) Catalytic oxidation: the gas, cooled to 400-450 °C, flows through a converter with 4 or 5 beds of V₂O₅ catalyst on silica support (pellets or rings). The reaction is exothermic and favored by low temperature but kinetics demand ~400 °C: 2 SO₂ + O₂ ⇌ 2 SO₃ (ΔH = −198 kJ/mol). Intercooling between beds resets equilibrium. Conversion reaches 99.7 % with double absorption (DCDA — Double Contact Double Absorption). (3) Absorption: SO₃ cannot be absorbed directly in water (forms uncontainable aerosols). It is absorbed in 98 % concentrated H₂SO₄, forming oleum H₂S₂O₇, then diluted by controlled addition of water to give H₂SO₄ at the desired strength. The DCDA trick introduces two absorption stages to push final conversion beyond 99.7 % and minimize SO₂ stack emissions. The process is exothermic across the whole chain — a modern plant typically recovers 4-6 GJ/t of acid as high-pressure steam, sold off or used for power generation. It's one of the few industrial processes that produces net energy while making a chemical. World production ~270 Mt/year (2022), of which ~60 % goes to phosphate fertilizer manufacturing.

Key components

The role of each main part, and the elements / compounds it involves.

  • Sulfur burner

    Burns sprayed liquid sulfur to produce SO₂ at 10-12 vol %.

    Refractory cylindrical chamber where molten sulfur (~140 °C) is sprayed under preheated dry air. Combustion at 1000-1100 °C, controlled to stay low in N₂O and NOₓ. Outgoing gases at 1000 °C feed a waste-heat boiler producing HP steam before entering the converter.

    1000-1100 °C · gaz 10-12 % SO₂ · récupération vapeur HP

    See also :so2
  • V₂O₅ catalytic converter

    Oxidizes SO₂ to SO₃ over multiple beds, with intercooling between them.

    Vertical vessel 8-12 m in diameter, with 4-5 horizontal beds of V₂O₅ catalyst (~5 wt %) on silica, with alkali promoters (K₂SO₄, Cs₂SO₄ for downstream beds — lowers light-off T° to 380 °C). Conversion 60 % at bed 1, 85 % cumulative at bed 2, 95 % at bed 3, 98 % at bed 4. Intercoolers cool gases to ~430 °C before each bed.

    4-5 lits · V₂O₅ 5 % / SiO₂ · promoteurs Cs/K · refroidissement inter-lits

    See also :so2
  • SO₃ absorption tower

    Absorbs SO₃ in 98 % concentrated H₂SO₄, forming oleum and then acid.

    Tower with acid-resistant ceramic packing (bricks + Intalox saddles), wetted by 98 % H₂SO₄ at 70-80 °C. SO₃ + H₂SO₄ → H₂S₂O₇ (oleum); controlled water addition dilutes to 96 %, 98 % or 100 % depending on the target market. The DCDA double absorption inserts this tower between converter beds 3 and 4 to push overall conversion to 99.7-99.9 %.

    Garnissage céramique · H₂SO₄ 98 % · 70-80 °C · DCDA

    See also :h2so4
  • Waste-heat boiler

    Captures heat from exothermic steps and converts it to HP steam.

    Tubular stainless heat exchanger (T-22 or better) installed after the burner AND after each catalytic bed. Steam produced at ~40 bar / 400 °C, 4-6 GJ/t H₂SO₄. Often integrated in a cogeneration cycle that also generates electricity: the process becomes a net energy producer.

    ~40 bar / 400 °C · 4-6 GJ/t H₂SO₄ · cogénération possible

Physical and chemical principles

The fundamental laws that make this process possible — and the constraints they impose.

  • Kinetics / equilibrium trade-off (Le Chatelier)

    Oxidation SO₂ + ½ O₂ → SO₃ is exothermic: high T lowers equilibrium conversion, low T slows kinetics. Industrial solution: operate at ~430 °C for kinetics, cool to 400 °C between beds to reset equilibrium. Cesium promoters in downstream beds drop light-off T° to ~380 °C — the quiet lever that gains 2-3 % conversion at the tail.

    ΔH = −198 kJ/mol ; K_eq diminue quand T augmente
    Applies to components :convertisseur-v2o5
  • Indirect absorption (the aerosol trap)

    SO₃ + H₂O directly forms an ultra-fine H₂SO₄ mist (stable aerosol that passes through standard filters). By first absorbing in concentrated H₂SO₄ (forming liquid oleum H₂S₂O₇), then diluting with water, aerosol formation is bypassed. A conceptual innovation as important as catalysis itself.

    Applies to components :tour-absorption-so3

Compounds involved

World production

270 Mt/yr
2022

Main applications

  • Phosphate fertilizers (superphosphate, MAP/DAP)60 %
  • Metallurgy (Cu, Zn, Ni, U leaching)10 %
  • Organic chemistry and petrochemistry10 %
  • Pulp & paper, water treatment8 %
  • Lead-acid batteries, miscellaneous12 %

Residual emissions and fertilizer demand

Modern DCDA contact processes reach ~99.7 % conversion — about 3 kg of SO₂ vented per tonne of acid produced. Across 270 Mt/year, that's still ~810 kt SO₂/year released, contributing to regional acid rain. Recent plants add an alkaline scrubber downstream to drop below 0.5 kg/t. Upstream, phosphate fertilizer demand (~60 % of market) ties H₂SO₄ production to world agriculture — any drop in P demand (cf. planetary phosphorus limits) would impact the process.
  • Catalyseurs Cs-promus pour T° d'amorçage abaissée
  • Scrubber alcalin (Na₂CO₃) en cheminée → SO₂ < 0,5 kg/t
  • DCDA généralisé (>99,7 % de conversion)
  • Récupération massive de chaleur en vapeur cogénérée

History and discovery

Discovery year1831
First industrial deployment1881
Peregrine Phillips · Rudolf Knietsch (BASF)· Royaume-Uni / Allemagne
Sources
  • Ullmann's Encyclopedia of Industrial Chemistry — Sulfuric Acid
  • USGS Mineral Commodity Summaries — Sulfur
  • Davenport, W. — Sulfuric Acid Manufacture
  • International Fertilizer Association (IFA) — H₂SO₄ Statistics
Processes