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".
220 meters north of the intersection of Zhanqian Avenue and Lanzhou East Road in Jiaozhou City, Qingdao, Shandong Province, China.