CN107793305A - A kind of production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder - Google Patents
A kind of production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder Download PDFInfo
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- CN107793305A CN107793305A CN201610834928.9A CN201610834928A CN107793305A CN 107793305 A CN107793305 A CN 107793305A CN 201610834928 A CN201610834928 A CN 201610834928A CN 107793305 A CN107793305 A CN 107793305A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/86—Use of additives, e.g. for stabilisation
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
The present invention relates to a kind of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde raw powder's production technology.Sodium pyrosulfite, zinc powder, formalin are used as raw material, inorganic acid makees activator, One-step production sodium bisulphite formaldehyde (rongalite).When sodium bisulphite formaldehyde mass concentration is more than 400g/L, stop reaction, it is cooled to 40 46 DEG C, stratification, plate and frame filter press is filtered, and inorganic base is added in filtrate and settles 40 48h, the mother liquor after inorganic base is settled removes zinc, free formaldehyde is removed, is then concentrated by evaporation and obtains block sodium bisulphite formaldehyde.Block rongalite is crushed, filter residue high-temperature calcination production high-quality zinc oxide.Rongalite product stability prepared by this method is good, and the effective content of the rongalite Zn content in 97.0 99.2%, rongalite is 10 30ppm, and free formaldehyde content is 100 200ppm in rongalite.The particular/special requirement of the industries such as medicine, rubber can be met.Na2S2O5+2Zn+2HCHO+2H2O→2NaHSO2·HCHO·2H2O+2ZnO。
Description
Technical field
The present invention relates to a kind of production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde (rongalite), belongs to chemistry
Industrial technical field.
Background technology
Sodium bisulphite formaldehyde, also referred to as sodium formaldehyde sulphoxylate (NaHSO2 HCHO 2H2O), trade name carving is white
Block, there is very strong reproducibility, be a kind of very strong white chunks material of hygroscopicity, it is soluble in water, alcohol is slightly soluble in, is sodium hydrosulfite
Second generation product.Rongalite is widely used, and in China Synthetic Rubber Industry, can be used as the activator of low temperature emulsion butylbenzene；Printing
It is used as pulling color agent in dyer's industry；It is used as the antidote of mercury, bismuth, barium in medical industry；Reducing agent is used as in atomic energy industry.
Domestic production sodium bisulphite formaldehyde mainly has one-step method and three-step approach etc. at present.Three-step approach using zinc powder, sulfur dioxide, formaldehyde as
Raw material obtains sodium bisulphite formaldehyde through three-step reaction, and the method technological process is long, used device is more, complex operation, and produces
Cost is high, environmental pollution is more serious, so the large-scale promotion application of method receives a definite limitation.One-step method is with sodium pyrosulfite
(Na2S2O5), zinc powder, formaldehyde be raw material, (Huang Liqun, Chen Yi political affairs formaldehyde close time sulphur to single step reaction synthesis sodium bisulphite formaldehyde
The research inorganic chemicals industries of sour hydrogen clean production process of sodium, 2008,40 (1)：45-47；Tian Weijun, one-step synthesis methods of easily defending the country
The technical study and production practices modern chemical industries of sodium bisulphite formaldehyde, 2010,30 (3)：84-86).The reaction side of one-step method
Formula：
Na2S2O5+2Zn+2HCHO+2H2O→2NaHSO2·HCHO·2H2O+2ZnO
One-step method avoids directly makees raw material using dangerous higher sulfur dioxide, and total overall reaction is closed
Leniently carry out, production scene safety, do not endangered by formaldehyde and sulfur dioxide in reactor；The raw material availability of one-step method compared with
Height, waste yield is few, and waste, which is easily processed, reaches discharge standard.
Patent《The preparation method of low-zinc sodium bisulphite formaldehyde》(application number 92108615.6) uses vulcanized sodium as precipitation
Agent, the rongalite zinc content of preparation is 30-50ppm.Patent《A kind of production method of rongalite with low zinc》(application number
200710023919.2) aluminium salt is used as precipitating reagent, and the rongalite zinc content of preparation is also up to 30-50ppm.Patent《It is a kind of
The method for preparing low zinc low iron clarification rongalite》(application number 200810143243.5) is using quinolines organic precipitant precipitation carving
Zinc, iron ion in white block solution, the rongalite zinc content of preparation, iron-holder are less than 10ppm.But above-mentioned patent mainly for
The rongalite of three-step approach production, also without relevant One-step production low content of free formaldehyde low-zinc sodium bisulphite formaldehyde (rongalite)
Method.
Contain a certain amount of zinc ion (100-300ppm) in the rongalite powder obtained using one-step synthesis method and dissociate
Formaldehyde (800-1000ppm), it is set to be restricted in some special application fields (such as medical treatment, rubber industry).Reduce carving
Zinc content and free formaldehyde content in white block, it should try to remove unnecessary zinc ion before rongalite solution concentration obtained by synthesis
And free formaldehyde.
The content of the invention
It is an object of the invention to provide the side that one kind prepares low content of free formaldehyde low-zinc sodium bisulphite formaldehyde (rongalite)
Method, rongalite product stability prepared by this method is good, and the effective content of the rongalite zinc in 97.0-99.2%, rongalite contains
Measure as 10-30ppm, free formaldehyde content is 100-200ppm in rongalite.It can meet that the special of the industries such as medicine, rubber will
Ask.
A kind of production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder, it is characterized in that being walked using following technique
It is rapid to complete：
1st, in the stainless steel cauldron stirred with anchor formula, sodium pyrosulfite, water, zinc powder, formalin are used as original
Material, inorganic acid make activator, One-step production sodium bisulphite formaldehyde (rongalite)；Connected between reacting in closed stirred tank
Enter steam and carry out heating response, NaHSO2·HCHO·2H2When O mass concentrations are more than 400g/L, stop reaction, pressed from both sides to reactor
The logical cooling water temperature of set is to 40-46 DEG C.Continue to stir 30min, stop reaction, stratification.Material send plate and frame filter press to filter,
Filtrate send mother liquor tank, adds inorganic base sedimentation 40-48h, and the mother liquor after inorganic base is settled adds chelating agent and removed in rongalite
Remaining zinc, add organic base and remove free formaldehyde in rongalite, then mother liquid evaporation is concentrated to give block sodium bisulphite first
Aldehyde (rongalite).Block rongalite is crushed, 50-60 revs/min of pulverizer rotating speed.Filter residue high-temperature calcination produces zinc oxide, oxidation
Zinc product mass fraction 99.5%-99.7%.
2nd, at 0~6 DEG C, in the stainless steel cauldron stirred with anchor formula, deionized water and sodium pyrosulfite are added
(Na2S2O5) or sodium hydrogensulfite, start stirring, rotating speed control is dissolved completely in 100~150r/min, sodium pyrosulfite
In deionized water.Wherein the mol ratio of deionized water and sodium pyrosulfite is n (H2O)∶n(Na2S2O5)≈(15-30)∶1.Or
Add the sodium hydrogensulfite of equimolar amounts.
3rd, in above-mentioned stainless steel cauldron, adding zinc powder, (zinc mass fraction >=94%, granularity are 36~45 μm of zinc powder
It is preferable to make raw material effect).Activator is made using inorganic acid, the oxide-film on zinc powder surface is peeled off, makes zinc powder activity recovery, is activated
Agent selects oxalic acid, citric acid, lactic acid, tartaric acid, one kind or two of which mixture of sulphoxylic acid.Wherein activator and zinc powder
Mass ratio is m (zinc powder): m (activator) ≈ (40-50): 1.The pH for controlling reaction mixture simultaneously is 3.0~4.0, activation temperature
35 DEG C~50 DEG C of degree, it is incubated 30~40min.n(Na2S2O5)∶n(Zn)≈1∶(2.0-2.8)。
4th, in above-mentioned stainless steel cauldron, the formalin of mass fraction 37% or the poly of equimolar number are added
Formaldehyde, n (Na2S2O5)∶n(CH2O) ≈ 1: (2.0-2.2), temperature control are incubated 20-40min at 42~58 DEG C.
5th, in above-mentioned stainless steel cauldron, steam heating response kettle is passed through, is warming up to 55 DEG C~70 DEG C, controls temperature,
It is incubated 10-20min.95~102 DEG C are continuously heating to, is incubated 90~120min.In the process, determined every 20min
NaHSO2·HCHO·2H2O content, mass concentration stop insulation when being more than 400g/L, lead to cooling water temperature to 40-46 DEG C.After
Continuous stirring 30min, stops stirring, closes cooling water, stratification.
6th, plate and frame filter press is sent to filter material in aforesaid reaction vessel, filtrate send mother liquor tank, adds inorganic base sedimentation 40-
48h, then vapo(u)rization system is sent through secondary filter, filter cake is washed using 4-6 set of deionized water, and washing lotion is reclaimed (when in last 1 washing lotion
NaHSO2·HCHO·2H2O mass concentrations are less than 1.0g/L can qualified discharge), send mother liquor tank to add inorganic base sedimentation in the lump.
When the 7th, settling the inorganic base that selects be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acid carbonate, vulcanized sodium, curing
The mass ratio of one or two kinds of mixtures of sodium, sodium pyrosulfite and inorganic base is m (sodium pyrosulfite): m (inorganic base) ≈ 1:
(0.003-0.005).The pH of mixed liquor is 11.0~12.0.
8th, the mother liquid evaporation concentration after inorganic base is settled.After mother liquor and washing lotion sedimentation are qualified, filtered through plate and frame filter press
Head tank is sent, is fed into evaporator, it is 60~70 DEG C, 0.08~0.1MPa of vacuum to control evaporating temperature, concentration time 30
~50min.After solution concentration reaches requirement in evaporator, crystallisation by cooling in aluminium groove is put into, produces rongalite product.Rongalite
Effective content in 97.0-99.2%.
9th, add chelating agent and remove zinc remaining in rongalite, the chelating agent added is disodium ethylene diamine tetraacetate, fourth
The matter of alkane tetrabasic carboxylic acid, sodium oxalate, sodium citrate, sodium tartrate, potassium oxalate, potassium citrate, potassium tartrate, rongalite and chelating agent
It is m (rongalite): m (chelating agent) ≈ 1: (0.01-0.02) to measure ratio.Zn content is 10-30ppm in rongalite.
10th, add organic base remove rongalite in free formaldehyde, the organic base added be piperidines, triethylamine, monoethanolamine,
The mass ratio of diethanol amine, triethanolamine, diethylenetriamine, triethylene tetramine, rongalite and organic base is m (rongalite): m
(organic base) ≈ 1: (0.006-0.018).Free formaldehyde content is 100-200ppm in rongalite.
11st, block rongalite is crushed, 50-60 revs/min of pulverizer rotating speed.
12nd, filter residue high-temperature calcination is produced into zinc oxide, for control calcining heat at 800~900 DEG C, calcination time is 2~3h.
Filter residue main component is ZnO and Zn (OH)2, calcine production and obtain zinc oxide product.Zinc oxide product mass fraction 99.5%-
99.7%.
Advantages of the present invention
1st, using sodium pyrosulfite (or sodium hydrogensulfite), water, zinc powder, formalin as raw material, inorganic acid makees activator, and one
Footwork production sodium bisulphite formaldehyde (rongalite), the effective content of rongalite is in 97.0-99.2%, zinc oxide product quality point
Number 99.5%-99.7%.
2nd, inorganic base sedimentation is selected, production cost is low, easily controllable；
3rd, add chelating agent and remove zinc remaining in rongalite, Zn content is 10-30ppm in rongalite.
4th, add organic base and remove free formaldehyde in rongalite, free formaldehyde content is 100-200ppm in rongalite.
5th, it disclosure satisfy that some special application fields contain (such as medical treatment, rubber industry) to rongalite zinc content and free formaldehyde
The high request of amount.
Embodiment
The present invention is described in further detail with reference to embodiment, but the embodiment invented is not limited to this.
Embodiment 1
At 4~6 DEG C, in the stainless steel cauldron stirred with anchor formula, 100 kilograms of deionized waters of addition, 50 kilograms
Sodium pyrosulfite (Na2S2O5), start stirring, rotating speed control is dissolved completely in deionized water in 120r/min, sodium pyrosulfite
In.
In above-mentioned stainless steel cauldron, add 45 kilograms of zinc powders (mass fraction 95%, granularity are 40 μm).Add 1.5
Kilogram oxalic acid makees activator, peels off the oxide-film on zinc powder surface, makes zinc powder activity recovery, while controls the pH of reaction mixture to be
3.4,45 DEG C of activation temperature, it is incubated 40min.
In above-mentioned stainless steel cauldron, the formalin of 40 kilograms of mass fractions 37% is added, temperature control is 48
DEG C, it is incubated 30min.
In above-mentioned stainless steel cauldron, steam heating response kettle is passed through, is warming up to 65 DEG C, controls temperature, insulation
15min.100 DEG C are continuously heating to, is incubated 100min.In the process, NaHSO is determined every 20min2·HCHO·2H2O's
Content, mass concentration stop insulation when being more than 400g/L, lead to cooling water temperature to 45 DEG C.Continue to stir 30min, stop stirring,
Close cooling water, stratification.
Plate and frame filter press is sent to filter material in aforesaid reaction vessel, filtrate send mother liquor tank, adds 2 kilograms of sodium hydroxide sedimentations
42h, the pH of mixed liquor is 11.0~12.0.Vapo(u)rization system is sent through secondary filter again, filter cake is washed using 4 sets of deionized water, washed
Liquid reclaims, and send mother liquor tank to add sodium hydroxide sedimentation in the lump.
Mother liquid evaporation concentration after sodium hydroxide is settled.It is 68 DEG C, vacuum 0.1MPa to control evaporating temperature, during concentration
Between 30min.After solution concentration reaches requirement in evaporator, crystallisation by cooling in aluminium groove is put into, produces rongalite product.Rongalite
Effective content 98.0%.
Add 0.2 kilogram of chelating agent disodium ethylene diamine tetraacetate and remove zinc remaining in rongalite, Zn content in rongalite
For 10-30ppm.Add 0.3 kilogram of organic base triethanolamine and remove free formaldehyde in rongalite, free formaldehyde content in rongalite
For 100-200ppm.
Block rongalite is crushed, 50-60 revs/min of pulverizer rotating speed.Filter residue high-temperature calcination is produced into zinc oxide, control is forged
Temperature is burnt at 880 DEG C, calcination time 2h.Zinc oxide product mass fraction 99.5%-99.7%.
Embodiment 2
At 4~6 DEG C, in the stainless steel cauldron stirred with anchor formula, 100 kilograms of deionized waters of addition, 52 kilograms
Sodium pyrosulfite (Na2S2O5), start stirring, rotating speed control is dissolved completely in deionized water in 130r/min, sodium pyrosulfite
In.
In above-mentioned stainless steel cauldron, add 46 kilograms of zinc powders (mass fraction 95%, granularity are 40 μm).Add 1.6
Kilogram oxalic acid makees activator, peels off the oxide-film on zinc powder surface, makes zinc powder activity recovery, while controls the pH of reaction mixture to be
3.3,42 DEG C of activation temperature, it is incubated 45min.
In above-mentioned stainless steel cauldron, the formalin of 41 kilograms of mass fractions 37% is added, temperature control is 50
DEG C, it is incubated 35min.
In above-mentioned stainless steel cauldron, steam heating response kettle is passed through, is warming up to 65 DEG C, controls temperature, insulation
15min.102 DEG C are continuously heating to, is incubated 100min.In the process, NaHSO is determined every 20min2·HCHO·2H2O's
Content, mass concentration stop insulation when being more than 400g/L, lead to cooling water temperature to 45 DEG C.Continue to stir 35min, stop stirring,
Close cooling water, stratification.
Plate and frame filter press is sent to filter material in aforesaid reaction vessel, filtrate send mother liquor tank, adds 2.1 kilograms of potassium hydroxide and sinks
42h drops, and the pH of mixed liquor is 11.0~12.0.Vapo(u)rization system is sent through secondary filter again, filter cake is washed using 4 sets of deionized water,
Washing lotion reclaims, and send mother liquor tank to add potassium hydroxide sedimentation in the lump.
Mother liquid evaporation concentration after potassium hydroxide is settled.It is 70 DEG C, vacuum 0.09MPa to control evaporating temperature, concentration
Time 30min.After solution concentration reaches requirement in evaporator, crystallisation by cooling in aluminium groove is put into, produces rongalite product.Carving is white
The effective content of block is 98.6%.
Add 0.2 kilogram of chelating agent disodium ethylene diamine tetraacetate and remove zinc remaining in rongalite, Zn content in rongalite
For 10-30ppm.Add 0.2 kilogram of organic base diethylenetriamine and remove free formaldehyde in rongalite, free formaldehyde contains in rongalite
Measure as 100-200ppm.
Block rongalite is crushed, 60 revs/min of pulverizer rotating speed.Filter residue high-temperature calcination is produced into zinc oxide, control calcining
Temperature is at 890 DEG C, calcination time 2h.Zinc oxide product mass fraction 99.7%.
Embodiment 3
At 4 DEG C, in the stainless steel cauldron stirred with anchor formula, 100 kilograms of deionized waters are added, 48 kilograms burnt sub-
Sodium sulphate (Na2S2O5), start stirring, rotating speed control is dissolved completely in deionized water in 120r/min, sodium pyrosulfite.
In above-mentioned stainless steel cauldron, add 44 kilograms of zinc powders (mass fraction 95%, granularity are 40 μm).Add 2.0
Kilogram citric acid makees activator, peels off the oxide-film on zinc powder surface, makes zinc powder activity recovery, while control the pH of reaction mixture
For 3.5,45 DEG C of activation temperature, 40min is incubated.
In above-mentioned stainless steel cauldron, the formalin of 39 kilograms of mass fractions 37% is added, temperature control is 48
DEG C, it is incubated 30min.
In above-mentioned stainless steel cauldron, steam heating response kettle is passed through, is warming up to 70 DEG C, controls temperature, insulation
15min.102 DEG C are continuously heating to, is incubated 100min.In the process, NaHSO is determined every 20min2·HCHO·2H2O's
Content, mass concentration stop insulation when being more than 400g/L, lead to cooling water temperature to 45 DEG C.Continue to stir 30min, stop stirring,
Close cooling water, stratification.
Plate and frame filter press is sent to filter material in aforesaid reaction vessel, filtrate send mother liquor tank, adds 1.9 kilograms of vulcanized sodium sedimentations
42h, the pH of mixed liquor is 11.0.Vapo(u)rization system is sent through secondary filter again, filter cake is washed using 4 sets of deionized water, washing lotion recovery,
Mother liquor tank is sent to add vulcanized sodium sedimentation in the lump.
Mother liquid evaporation concentration after vulcanized sodium is settled.It is 70 DEG C, vacuum 0.1MPa to control evaporating temperature, concentration time
30min.After solution concentration reaches requirement in evaporator, crystallisation by cooling in aluminium groove is put into, produces rongalite product.Rongalite
Effective content is 98.0%.
Add 0.4 kilogram of chelating agent sodium oxalate and remove zinc remaining in rongalite, Zn content is 30ppm in rongalite.Add
Enter 0.5 kilogram of organic base diethanol amine and remove free formaldehyde in rongalite, free formaldehyde content is 150ppm in rongalite.
Block rongalite is crushed, 50-60 revs/min of pulverizer rotating speed.Filter residue high-temperature calcination is produced into zinc oxide, control is forged
Temperature is burnt at 890 DEG C, calcination time 2h.Zinc oxide product mass fraction 99.7%.
Embodiment 4
At 4 DEG C, in the stainless steel cauldron stirred with anchor formula, 100 kilograms of deionized waters, 95 kilograms of sulfurous are added
Sour hydrogen sodium, starts stirring, and rotating speed control is dissolved completely in deionized water in 120r/min, sodium hydrogensulfite.
In above-mentioned stainless steel cauldron, add 46 kilograms of zinc powders (mass fraction 95%, granularity are 40 μm).Add 1.4
Kilogram oxalic acid makees activator, peels off the oxide-film on zinc powder surface, makes zinc powder activity recovery, while controls the pH of reaction mixture to be
3.5,45 DEG C of activation temperature, it is incubated 30min.
In above-mentioned stainless steel cauldron, the formalin of 40 kilograms of mass fractions 37% is added, temperature control is 48
DEG C, it is incubated 30min.
In above-mentioned stainless steel cauldron, steam heating response kettle is passed through, is warming up to 68 DEG C, controls temperature, insulation
15min.100 DEG C are continuously heating to, is incubated 120min.In the process, NaHSO is determined every 20min2·HCHO·2H2O's
Content, mass concentration stop insulation when being more than 400g/L, lead to cooling water temperature to 45 DEG C.Continue to stir 30min, stop stirring,
Close cooling water, stratification.
Plate and frame filter press is sent to filter material in aforesaid reaction vessel, filtrate send mother liquor tank, adds 1.7 kilograms of vulcanized sodium sedimentations
42h, the pH of mixed liquor is 11.0.Vapo(u)rization system is sent through secondary filter again, filter cake is washed using 4 sets of deionized water, washing lotion recovery,
Mother liquor tank is sent to add vulcanized sodium sedimentation in the lump.
Mother liquid evaporation concentration after vulcanized sodium is settled.It is 68 DEG C, vacuum 0.1MPa to control evaporating temperature, concentration time
30min.After solution concentration reaches requirement in evaporator, crystallisation by cooling in aluminium groove is put into, produces rongalite product.Rongalite
Effective content is 98.6%.
Add 0.4 kilogram of chelating agent sodium oxalate and remove zinc remaining in rongalite, Zn content is 30ppm in rongalite.Add
Enter 0.5 kilogram of organic base triethanolamine and remove free formaldehyde in rongalite, free formaldehyde content is 160ppm in rongalite.
Block rongalite is crushed, 50-60 revs/min of pulverizer rotating speed.Filter residue high-temperature calcination is produced into zinc oxide, control is forged
Temperature is burnt at 890 DEG C, calcination time 2h.Zinc oxide product mass fraction 99.5%.
Embodiment 5
At 4 DEG C, in the stainless steel cauldron stirred with anchor formula, 100 kilograms of deionized waters are added, 48 kilograms burnt sub-
Sodium sulphate (Na2S2O5), start stirring, rotating speed control is dissolved completely in deionized water in 120r/min, sodium pyrosulfite.
In above-mentioned stainless steel cauldron, add 45 kilograms of zinc powders (mass fraction 96%, granularity are 40 μm).Add 1.4
Kilogram sulphoxylic acid makees activator, peels off the oxide-film on zinc powder surface, makes zinc powder activity recovery, while control the pH of reaction mixture
For 3.6,45 DEG C of activation temperature, 30min is incubated.
In above-mentioned stainless steel cauldron, the formalin of 41 kilograms of mass fractions 37% is added, temperature control is 48
DEG C, it is incubated 30min.
In above-mentioned stainless steel cauldron, steam heating response kettle is passed through, is warming up to 68 DEG C, controls temperature, insulation
15min.100 DEG C are continuously heating to, is incubated 100min.In the process, NaHSO is determined every 20min2·HCHO·2H2O's
Content, mass concentration stop insulation when being more than 400g/L, lead to cooling water temperature to 45 DEG C.Continue to stir 30min, stop stirring,
Close cooling water, stratification.
Plate and frame filter press is sent to filter material in aforesaid reaction vessel, filtrate send mother liquor tank, adds 1.6 kilograms of vulcanized sodium sedimentations
42h, the pH of mixed liquor is 11.0.Vapo(u)rization system is sent through secondary filter again, filter cake is washed using 4 sets of deionized water, washing lotion recovery,
Mother liquor tank is sent to add vulcanized sodium sedimentation in the lump.
Mother liquid evaporation concentration after vulcanized sodium is settled.It is 68 DEG C, vacuum 0.1MPa to control evaporating temperature, concentration time
30min.After solution concentration reaches requirement in evaporator, crystallisation by cooling in aluminium groove is put into, produces rongalite product.Rongalite
Effective content is 98.4%.
Add 0.2 kilogram of chelating agent sodium ethylene diamine tetracetate and remove zinc remaining in rongalite, Zn content is in rongalite
20ppm.Add 0.5 kilogram of organic base triethanolamine and remove free formaldehyde in rongalite, free formaldehyde content is in rongalite
160ppm。
Block rongalite is crushed, 50-60 revs/min of pulverizer rotating speed.Filter residue high-temperature calcination is produced into zinc oxide, control is forged
Temperature is burnt at 890 DEG C, calcination time 2h.Zinc oxide product mass fraction 99.5%.
Claims (12)
1. in the stainless steel cauldron stirred with anchor formula, sodium pyrosulfite, water, zinc powder, formalin are used as raw material, nothing
Machine acid makees activator, One-step production sodium bisulphite formaldehyde (rongalite)；Reaction is passed through steaming indirectly in closed stirred tank
Vapour carries out heating response, sampling analysis, NaHSO2·HCHO·2H2O mass concentrations are reacted and terminated after being more than 400g/L, to reaction
Kettle chuck leads to cooling water temperature to 40-46 DEG C.Continue to stir 30min, stop stirring, close cooling water, stratification.Material send plate
Frame filter press filters, and filtrate send mother liquor tank, adds inorganic base sedimentation 40-48h, mother liquor, washing lotion evaporation after inorganic base is settled
Concentration.Add chelating agent and remove zinc remaining in rongalite, add organic base and remove free formaldehyde in rongalite, bulk carving is white
Block crushes, 50-60 revs/min of pulverizer rotating speed.The effective content of rongalite Zn content in 97.0-99.2%, rongalite is 10-
30ppm, free formaldehyde content is 100-200ppm in rongalite.Filter residue high-temperature calcination produces zinc oxide, zinc oxide product quality
Fraction 99.5%-99.7%.
2. the production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder as described in right 1, it is characterised in that 0~6
DEG C when, in the stainless steel cauldron stirred with anchor formula, add deionized water and sodium pyrosulfite (Na2S2O5) or sulfurous
Sour hydrogen sodium, starts stirring, and rotating speed control is dissolved completely in deionized water in 100~150r/min, sodium pyrosulfite.Wherein go
The mol ratio of ionized water and sodium pyrosulfite is n (H2O)∶n(Na2S2O6)≈(15-30)∶1.Or add the Asia of equimolar amounts
Niter cake.
3. the production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder as described in right 1, it is characterised in that above-mentioned
In stainless steel cauldron, add zinc powder (zinc mass fraction >=94%, granularity are 36~45 μm).Activator is made using inorganic acid,
The oxide-film on zinc powder surface is peeled off, makes zinc powder activity recovery, inorganic acid activators select oxalic acid, citric acid, lactic acid, winestone
Acid, one kind or two of which mixture of sulphoxylic acid.Wherein the mass ratio of activator and zinc powder is m (zinc powder): m (activator) ≈
(40-50)∶1.The pH for controlling reaction mixture simultaneously is 3.0~4.0,35 DEG C~50 DEG C of activation temperature, is incubated 30~40min.n
(Na2S2O5)∶n(Zn)≈1∶(2.0-2.8)。
4. the production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder as described in right 1, it is characterised in that above-mentioned
In stainless steel cauldron, the formalin of mass fraction 37% or the paraformaldehyde of equimolar number, n (Na are added2S2O5)∶n
(CH2O) ≈ 1: (2.0-2.2), temperature control are incubated 20-40min at 42~58 DEG C.
5. the production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder as described in right 1, it is characterised in that above-mentioned
In stainless steel cauldron, steam heating response kettle is passed through, is warming up to 55 DEG C~70 DEG C, controls temperature, is incubated 10-20min.Continue
95~102 DEG C are warming up to, is incubated 90~120min.In the process, NaHSO is determined every 20min2·HCHO·2H2O's contains
Amount, mass concentration stop insulation when being more than 400g/L, lead to cooling water temperature to 40-46 DEG C.Continue to stir 30min, stop stirring,
Close cooling water, stratification.
6. the production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder as described in right 1, it is characterised in that will be above-mentioned
Material in reactor send plate and frame filter press to filter, and filtrate send mother liquor tank, adds inorganic base sedimentation 40-48h, then send through secondary filter
Vapo(u)rization system, filter cake are washed using 4-6 set of deionized water, and washing lotion is reclaimed (as NaHSO in last 1 washing lotion2·HCHO·2H2O
Mass concentration is less than 1.0g/L can qualified discharge), send mother liquor tank to add inorganic base sedimentation in the lump.
7. the sedimentation method as described in right 6, it is characterised in that inorganic base is sodium hydroxide, potassium hydroxide, sodium carbonate, bicarbonate
The mass ratio of sodium, vulcanized sodium, one or two kinds of mixtures of sodium disulfide, sodium pyrosulfite and inorganic base is m (pyrosulfurous acids
Sodium): m (inorganic base) ≈ 1: (0.003-0.005).The pH of mixed liquor is 11.0~12.0.
8. the production method of sodium bisulphite formaldehyde powder as described in right 6, it is characterised in that the mother after inorganic base is settled
Liquid, washing lotion are concentrated by evaporation.After mother liquor and washing lotion sedimentation is qualified, head tank is sent through plate and frame filter press filtering, is fed into evaporator,
It is 60~70 DEG C, 0.08~0.1MPa of vacuum, 30~50min of concentration time to control evaporating temperature.When solution is dense in evaporator
After contracting reaches requirement, crystallisation by cooling in aluminium groove is put into, produces rongalite product.The effective content of rongalite is in 97.0-99.2%.
9. the production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder as described in right 1, it is characterised in that add chela
Mixture removes remaining zinc in rongalite, the chelating agent added be disodium ethylene diamine tetraacetate, BTCA, sodium oxalate,
The mass ratio of sodium citrate, sodium tartrate, potassium oxalate, potassium citrate, potassium tartrate, rongalite and chelating agent is m (rongalite):
M (chelating agent) ≈ 1: (0.01-0.02).Zn content is 10-30ppm in rongalite.
10. the production method of low content of free formaldehyde low-zinc sodium bisulphite formaldehyde powder as described in right 1, it is characterised in that add
Organic base removes free formaldehyde in rongalite, and the organic base added is piperidines, triethylamine, monoethanolamine, diethanol amine, three ethanol
The mass ratio of amine, diethylenetriamine, triethylene tetramine, rongalite and organic base is m (rongalite): m (organic base) ≈ 1:
(0.006-0.018).Free formaldehyde content is 100-200ppm in rongalite.
11. the production method of low zinc low content of free formaldehyde sodium bisulphite formaldehyde powder as described in right 1, it is characterised in that by bulk
Rongalite crushes, 50-60 revs/min of pulverizer rotating speed.
12. the production method of low zinc low content of free formaldehyde sodium bisulphite formaldehyde powder as described in right 1, it is characterised in that will weigh
The filter residue high-temperature calcination production zinc oxide of the gained of profit 6, for control calcining heat at 800~900 DEG C, calcination time is 2~3h.Filter residue
Main component is ZnO and Zn (OH)2, calcine production and obtain zinc oxide product.Zinc oxide product mass fraction 99.5%-
99.7%.
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| CN116102471A (en) * | 2023-02-16 | 2023-05-12 | 湖南特俪洁新材料科技有限公司 | Preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate |
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| CN109265379A (en) * | 2018-09-27 | 2019-01-25 | 湖南中翔化学科技有限公司 | A kind of preparation method of no free formaldehyde and stable storing rongalite |
| CN109265379B (en) * | 2018-09-27 | 2021-01-19 | 湖南中翔化学科技有限公司 | Preparation method of free formaldehyde-free and storage-stable rongalite |
| CN111646886A (en) * | 2020-07-03 | 2020-09-11 | 沈阳双鼎制药有限公司 | Preparation method of low-zinc sodium formaldehyde sulfoxylate |
| CN116102471A (en) * | 2023-02-16 | 2023-05-12 | 湖南特俪洁新材料科技有限公司 | Preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate |
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