A Study on the Treatment of

Formaldehyde Wastewater by
Addition Reaction
Dongmei et. al (2010)

Pamor, Emeliza M.
ABSTRACT
❖ Two procedures used in the experiment to achieve the best experimental
factors are the single-factor and the orthogonal experiment.
❖ Initial concentration of formaldehyde was 120 mg/L that reacted within 30
minutes which resulted to 3:1 ratio of NaHSO3 and HCHO with 100%
removal rate and fully satisfied the national emission standards
(concentration of formaldehyde ≤ 1 mg/L).
❖ The tannery wastewater was also tested with the initial concentration of 120
mg/L and reacted to sodium bisulfate proceeded to 0.446 mg/L at 30
minutes reaction time which also satisfied the national emission standard.
INTRODUCTION
❖ Formaldehyde (HCHO) is a toxic substance and list as the
carcinogenic substance by World Health Organization.
❖ Formaldehyde is used in different variety of industrial
materials including:
1. Chemical
2. Organic synthesis
3. Pharmaceuticals
4. Paints and Coating
5. Plastics, Leather and Textiles
❖ Researchers from China studied different ways on how
to treat the formaldehyde wastewater coming from the
industrial plants in order for it to meet the dumping
standards.
❖ Main treatment methods: Fenton Photocatalytic
Oxidation, Wet Oxidation, Chlorine Dioxide, Steam
Stripping, Oxidation-adsorption
❖ The advanced oxidation processing is used as the
pretreatment technology for industrial formaldehyde
wastewater.
MATERIALS AND METHOD
ADDITION REACTION MECHANISM
❖ Formaldehyde addition reaction is a nucleophilic addition which is
the speed of nucleophiles is the determinant of reaction.
❖ It is a reversible reaction

➔ Decomposition of addition product releases the original HCHO by

acid or alkali.
EXPERIMENTAL METHOD
❖ Prepare 200ml of different concentration of formaldehyde solution in
250mL beaker.
❖ Add an amounts of sodium bisulfate ((NaHSO3) and continuously
mixed by magnetic stirring with pH set in neutral condition.
❖ Measure formaldehyde concentration at different temperature using
acetylacetone spectrophotometric.
 EXPERIMENTAL METHOD

The major factors in the single-factor experiment:

1. Amount of bisulfite
2. Reaction time
3.HCHO concentration
RESULTS AND DISCUSSION
 SINGLE-FACTOR EXPERIMENT
❖ 200ml of HCHO solution reacted with NaHSO3 at
25℃ and 30 mins reaction time.
❖ The removal rate of HCHO increases as the
NaHSO3 increases.
❖ 99.24% removal rate of formaldehyde achieved in
2:1 ratio of NaHSO3 to HCHO with 0.76 mg/L
HCHO meeting the national emission standard
(concentration of formaldehyde ≤ 1mg/L)
❖ 100% removal rate of formaldehyde in 3:1 ratio of
NaHSO3 to HCHO
SINGLE-FACTOR EXPERIMENT

❖ Initial concentration of HCHO are 80 mg/l, 100 mg/L and 120 mg/L.
❖ The reaction time was 10 mins, 20mins and 30 mins respectively.
❖ The reaction time increases as the removal rate increases.
❖ The removal rate of formaldehyde increases with respect to the
initial concentration of HCHO.
SINGLE-FACTOR EXPERIMENT

The increase in concentration of formaldehyde can increased the

effective collision between molecules which accelerates the rate of
reaction.
 ORTHOGONAL EXPERIMENT
❖ It was designed in order for more systematically and accurately test the
comprehensive effect and primary and secondary relationship factors.
❖ Addition reaction was controlled at neutral reaction condition
Major factors :
1. Amount of NaHSO3
2. Time
3. Initial concentration of HCHO
ORTHOGONAL EXPERIMENT
Reaction time and the
concentration are the same
in Single-factor experiment
but the ratio of NaHSO3 to
HCHO is 3:1 with nearly
100% removal rate of
formaldehyde.
 EXPERIMENT FOR INDUSTRY
WASTEWATER OF FORMALDEHYDE

❖ Complex wastewater containing formaldehyde solution with pure

reagents tested in industry wastewater of formaldehyde.
❖ Initial concentration (120 mg/L of HCHO) of tannery wastewater was
examined.
❖ At t=30 mins, the remaining concentration reduced to 0.446 mg/L.
 EXPERIMENT FOR INDUSTRY
WASTEWATER OF FORMALDEHYDE

The graph shows that concentration of formaldehyde is in reduction trend

caused by the excessive amount of sodium bisulfite (NaHSO3).
 EXPERIMENT FOR INDUSTRY
WASTEWATER OF FORMALDEHYDE
❖ The initial CODCr (conversion of chemical oxygen) is
757.89mg/L in wastewater, at t=30 mins it becomes 801.54
mg/L caused by the excessive amount of NaHSO3 in the
process of addition reaction.
❖ The remaining was reacted with potassium dichromate.
❖ DEMAND measurement with the combination of dichromate,
sulfuric acid and heat to oxidise the solution.
➔ Figure shows concentration of remaining CODCr vs.time
CONCLUSION
The process was practicable which satisfied the national
emission standard of formaldehyde (concentration ≤ 1 mg/L).
The reaction was characterized by fast response and highly
reduction rate. For the best addition reaction it must be in the
neutral reaction condition. The process results to 99% removal
rate with the ratio of 2:1 of NaHSO3 to HCHO at 30 mins
reaction time and also the value of pH on NaHSO3 was highly
considered.