This system validated the applicability of "triple-effect co-current + TVR + OSLO crystallization" in vitamin high-sulfate wastewater at a scale of 12.5t/h. The steam consumption, salt quality, and mother liquor volume were all better than the industry average, providing a replicable and scalable zero-emission template for sub-sectors such as vitamins, antibiotics, and steroids.
I. Project Background
A vitamin B5 production base produces 8000t of calcium pantothenate annually, discharging 300m³ of process mother liquor daily. This mother liquor contains 10-12% Na₂SO₄, trace amounts of pantothenic acid, COD 25000-35000mg/L, and pH 4.5. The original triple-effect evaporation + centrifugal process consumed 0.42kg/kg of water steam, and the sodium sulfate purity was only 93%, failing to meet usage standards. Furthermore, outsourcing the centrifugation mother liquor cost as high as 420 RMB/t. In 2024, the company plans to construct a new 12.5t/h triple-effect evaporation crystallization system with the following targets: steam consumption ≤0.28kg/kg water, anhydrous sodium sulfate byproduct ≥99%, and mother liquor volume ≤2%.
II. Process Route
2.1 Process Overview
The process consists of five stages: neutralization and degassing → triple-effect co-current falling film concentration → OSLO forced circulation crystallization → thickening centrifugation → mother liquor drying. The main body is made of 2205 duplex stainless steel, and the surfaces in contact with the materials are electrolytically polished to Ra≤0.4μm.
Pretreatment: Wastewater is adjusted to pH 7.0 with NaOH, and vacuum degassed at 50℃ to recover CO₂ and light COD components. Secondary steam undergoes acid washing and activated carbon fiber adsorption, reducing VOCs by 90%.
Triple-effect co-current: Live steam at 0.5MPa 152℃ enters the shell side of effect I, with a boiling point of 120℃; secondary steam sequentially enters effect II 95℃ and effect III 68℃, -0.073MPa, with an overall specific heat transfer coefficient of 1850W/m²·K.
Crystallization Separation: The output concentration of the III-effect crystallizer is 28%, pumped into an OSLO-type forced circulation crystallizer at an operating temperature of 80℃, with a crystal slurry density of 25%. After washing and classification, particles with a D500.45mm diameter are obtained. A two-stage piston pusher centrifuge has a processing capacity of 6 t/h of salt, with a wet salt moisture content ≤3%.
Mother Liquor Drying: The centrifuged mother liquor has a COD of 120,000 mg/L. After passing through a paddle dryer, 0.8 t/h of mixed salt with a moisture content of 5% is obtained and sent to hazardous waste incineration.
2.2 Key Equipment Parameters
Evaporation Capacity: 12.5 t/h --inlet water 11% salt content
Heat Exchange Area: Effect I 420 m², Effect II 380 m², Effect III 340 m²
Steam Consumption: 0.27 kg/kg water --including thermocompressor pump
Cooling Water Circulation: 140 m³/h 28→36℃
Vacuum System: Three-stage Roots + water ring, ultimate vacuum -0.085 MPa
III. Technological Innovations
3.1 Thermocompressor Steam Recompression TVR
Secondary steam from Effect I at 120℃ is pressurized to 135℃ by a 0.6 MPa power steam jet pump and reused in the shell side of Effect I, saving 22% of steam.
3.2 Sodium Sulfate Crystallization Control
Utilizing "80℃ high-temperature crystallization + graded washing" technology, the formation of decahydrate salt is suppressed, resulting in dense crystals with a whiteness of 88% and a purity of 99.2%.
3.3 Scale Prevention and CIP: The falling film pipe uses a Φ32×1.2mm internal groove pipe with a flow velocity of 2.0m/s, and the shear force inhibits calcium sulfate scale. Online CIP uses alternating cleaning with 3% NaOH + 2% HEDP chelating agent at 75℃, with a cycle of 12 days and a cleaning time of 4 hours.
3.4 Condensate Deep Treatment: Secondary condensate with a COD of 400~600mg/L is treated with catalytic ozone + BAF, resulting in an effluent COD ≤30mg/L and conductivity ≤80μS/cm. This effluent is then reused for boiler soft water makeup, achieving a reuse rate of 96%.
IV. Operational Data
Successful start-up on June 2024. 72-hour performance evaluation:
Evaporation rate: 12.7 t/h
Steam consumption: 0.265 kg/kg water
Anhydrous sodium sulfate production: 1.35 t/h
Unit availability: >99%
V. Economic and Environmental Benefits
5.1 Economic Indicators
Annual operating cost: RMB 2.85 million steam, electricity, chemicals.
Annual savings in outsourced disposal fees: RMB 16.8 million;
Sales revenue from by-product sodium sulfate: RMB 5.2 million;
Annual net profit: RMB 19.15 million.
5.2 Environmental Indicators
Annual reduction of high-salinity wastewater discharge: 90,000 t; COD emission reduction: 2,700 t;
CO₂ emission reduction: 6,200 t/year;
600 t of hazardous waste salts incinerated in compliance with regulations, achieving "reduction and resource recovery".
No. 81, Fengfei Road, Beiguan Industrial Park, Jiaozhou City, Qingdao Province, China