CN113307289A - Resource recycling method for hazardous waste containing brominated alkanes - Google Patents
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- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Abstract
The application relates to the field of hazardous waste disposal and recycling, and particularly discloses a hazardous waste recycling method containing bromoalkane, which comprises the following steps: s1: alkali washing, namely adding alkali liquor into the dangerous waste to wash and absorb, and separating liquid to obtain alkali washing liquid and bromine-containing waste liquid; s2: hydrolyzing, namely adding a sodium hydroxide solution into the bromine-containing waste liquid for hydrolysis, and separating liquid to obtain a mixed solution; s3: separating alcohol from the mixed solution through pervaporation to obtain a salt solution, and combining the alkaline solution and the salt solution to obtain a combined solution; s4: and (4) carrying out membrane distillation on the combined solution until crystals appear, and drying the crystals to obtain the sodium bromide. The application has the effects of reducing equipment corrosion and realizing resource recovery in the treatment of the waste containing brominated alkanes.
Description
Technical Field
The application relates to the field of hazardous waste disposal and recycling, in particular to a hazardous waste recycling method containing brominated alkanes.
Background
Bromine is an important chemical raw material, and a wide variety of inorganic bromides, bromates and bromine-containing organic compounds derived from it have special value in national economy and scientific and technological development. Through the rapid development of the last decade and especially the last years, China makes great progress in the aspects of bromine series product production and technical development, and especially makes great progress in the aspects of inorganic bromide, bromine series flame retardant, medical intermediate and organic synthesis intermediate synthesis and the like.
The organic bromine series fine chemical products taking hydrogen bromide or bromine salt as main raw materials are widely applied to the fields of medicines, pesticides, dyes, spices, flame retardance, fire extinguishment, synthetic materials, electronic etching and the like, but a large amount of bromine-containing waste is often generated in the production process. Taking a bromine deep processing project of a certain chemical plant as an example, bromopropane is produced by synthesizing hydrogen bromide and propylene, a product is obtained after the bromopropane is rectified, and rectification residual liquid/slag is generated at the same time, belongs to dangerous waste and needs to be reasonably disposed.
At present, the main treatment mode of the rectification residual liquid/slag containing brominated alkanes is incineration treatment, and harmless treatment is realized by directly incinerating the rectification residual liquid/slag containing brominated alkanes.
Disclosure of Invention
In order to reduce equipment corrosion and realize resource recovery in the waste treatment of brominated alkanes, the application provides a resource recovery method for hazardous wastes containing brominated alkanes.
The application provides a hazardous waste resource recovery side who contains bromine substituted alkane adopts following technical scheme:
a resource recovery method for hazardous waste containing brominated alkanes comprises the following steps:
s1: alkali washing, namely adding alkali liquor into the dangerous waste to wash and absorb, and separating liquid to obtain alkali washing liquid and bromine-containing waste liquid;
s2: hydrolyzing, namely mixing the bromine-containing waste liquid with a sodium hydroxide solution and a catalyst, hydrolyzing, and separating liquid to obtain a mixed solution;
s3: separating alcohol from the mixed solution through pervaporation to obtain a salt solution, and combining the alkaline solution and the salt solution to obtain a combined solution;
s4: crystallizing the combined solution, and drying and crystallizing to obtain the sodium bromide.
By adopting the technical scheme, in the step of alkali washing, inorganic bromide ions in the hazardous waste enter alkali liquor to form sodium bromide;
and (3) a hydrolysis step, namely hydrolyzing the organic bromine in the hazardous waste, wherein the hydrolysis reaction is essentially: R-Br + H2O=ROH+HBr，HBr+NaOH=NaBr+H2O；
Separating out the product alcohol ROH of the hydrolysis reaction, and crystallizing to obtain sodium bromide, wherein R is an alkane group. After alcohol is separated from the mixed solution, the mixed solution is crystallized, so that reverse proceeding of hydrolysis balance is avoided, and the yield of sodium bromide is improved.
The original hazardous waste may contain organic bromine and inorganic bromine (namely bromide ions), and the method of firstly performing alkali washing and then performing hydrolysis is adopted to separate the inorganic bromide ions, so that the influence of the inorganic bromide ions on the subsequent hydrolysis reaction balance of the brominated alkanes in the bromine-containing waste liquid is avoided, and the method is favorable for the hydrolysis reaction of the brominated alkanes.
And (3) after hydrolysis in the step S2, sending the bottom insoluble liquid or solid separated in the liquid separation process to incineration treatment, sending the alcohol with more complex components obtained by pervaporation separation in the step S3 to incineration treatment, and reducing the incineration treatment part. And a large amount of corrosive intermediate products such as acid gas are not generated in the whole recovery process, so that the corrosion to equipment is reduced, and the recycled alcohol and sodium bromide products are obtained.
Preferably, in step S3, the alcohol is separated by distillation or pervaporation.
Further preferably, in step S3, the alcohol is separated by pervaporation.
By adopting the technical scheme, the mixed solution separated in the hydrolysis step is a water layer, and in the mixed solution, because the water solution of the alcohol can form azeotropy under a certain concentration, the separation is difficult to realize, and the alcohol in the mixed solution can be more completely separated out through pervaporation separation, so that the alcohol is obtained through separation. The quality of the obtained alcohol is uncertain due to different types, contents and the like of organic matters such as brominated alkanes in the hazardous waste, if the types of the brominated alkanes in the hazardous waste are single or the content of a certain brominated alkane is high, the content of a certain alcohol in the separated alcohol is high, the separated alcohol can be sold as a product, and when the components of the alcohol are complex, the alcohol can be directly sent to incineration treatment. Finally, the sodium bromide crystal product is obtained through membrane separation and crystallization and can be sold as a product.
In one embodiment, the alcohol is separated in step S3 using distillation.
Preferably, the distillation conditions are between 90 and 100 ℃.
Until no more condensed liquid is produced, the distillation is ended.
Preferably, the alkali liquor in the alkali washing step is an aqueous sodium hydroxide solution.
Preferably, the alkali liquor in the alkali washing step is 5wt% to 10wt% of sodium hydroxide solution.
Preferably, in the alkaline washing, the molar ratio of the sodium hydroxide to the inorganic bromide ions is (1-2): 1.
preferably, in the alkaline washing, the molar ratio of the sodium hydroxide to the inorganic bromide ions is (1.1-1.2): 1.
preferably, the alkali washing is performed at normal temperature.
Preferably, alkali liquor is added into the dangerous waste for washing and absorption, then the dangerous waste is kept stand for 30-60min and then liquid separation is carried out.
By adopting the technical scheme, the sodium hydroxide solution is selected in the alkaline washing process, so that inorganic bromide ions in the hazardous waste are dissolved in the sodium hydroxide solution, and the alkaline washing solution containing sodium bromide is obtained, and the recovery rate of bromine is favorably improved.
Meanwhile, by controlling the amount of the added sodium hydroxide, inorganic bromide ions can be sufficiently removed, which is beneficial to improving the conversion rate of the hydrolysis of bromoalkane in the bromine-containing waste liquid.
Preferably, the molar ratio of sodium hydroxide to organic bromine in the hydrolysis is (1-1.2): 1.
preferably, the hydrolysis conditions are: the temperature is 100 ℃ and 150 ℃, and the pressure is 0.1-1 Mpa.
Preferably, the catalyst is one or more of molecular sieve, alumina, copper oxide and molecular sieve-supported copper oxide.
Preferably, the amount of the catalyst is 4-8wt% of the bromine-containing waste liquid.
Preferably, the amount of the catalyst is 5wt% of the bromine-containing waste liquid.
Preferably, the hydrolysis time is 2-4 h.
By adopting the technical scheme, when the pH is 7-8, the sodium hydroxide completely reacts, and the hydrolysis is finished. Under the hydrolysis condition, the conversion rate of the hydrolysis of bromoalkane in the bromine-containing waste liquid is higher, and the yield of bromine is improved.
Preferably, the pervaporation is performed by using an organic membrane.
In one embodiment, the mixed solution is on the front side of the organic film, and the alcohol vapor is on the back side of the organic film.
The pressure of the alcohol vapor side is 0.05-0.09 MPa.
In one embodiment, the pervaporation is carried out at 60-100 ℃.
By adopting the technical scheme, the mixed solution containing sodium bromide and alcohol is vaporized by permeation, volatile component alcohol is vaporized into steam after flowing through the membrane, the vaporized steam is condensed by the condenser, and meanwhile, the negative pressure state of the alcohol vapor side is kept by using a vacuumizing mode, so that the permeation is continuously carried out until the alcohol is completely separated out.
Under this pervaporation condition, the pervaporation separation is ended until no condensate continues to be produced on the alcohol vapor side. The control of the pervaporation separation condition can separate the alcohol in the mixed solution more completely.
The pervaporation method can separate mixed substances with approximate boiling points or azeotropy, is suitable for separating volatile components in water, has little pollution and has economic and technical advantages.
Preferably, activated carbon is added to the combined solution for adsorption.
Preferably, the adding amount of the activated carbon in the combined solution is 0.1wt% to 0.5 wt%.
Preferably, the temperature of the activated carbon adsorption is 20-40 ℃.
Preferably, the adsorption time of the activated carbon is 30-60 min.
By adopting the technical scheme, impurities such as residual organic matters in the combined solution can be further adsorbed and removed under the limitation of the adsorption condition of the activated carbon, so that the color of the combined solution reaches a colorless transparent state, and the purity of a sodium bromide product is improved.
And under the temperature limit, residual organic matters in the combined solution can be better adsorbed, so that the purity of the sodium bromide product is favorably improved.
Alcohol is separated out in the pervaporation step, and then activated carbon is added for adsorption, so that excessive alcohol does not need to be adsorbed by the activated carbon in the pervaporation step, the addition amount of the activated carbon is small, and the activated carbon can better adsorb impurities such as residual organic matters.
Preferably, the crystallization in step S4 may be membrane distillation or evaporative crystallization.
In one embodiment, membrane distillation is used for crystallization.
Preferably, the cold side is 20-25 ℃ and the warm side is 40-80 ℃ during membrane distillation.
Preferably, the membrane distillation is terminated when a large amount of crystals precipitate in the combined solution during the membrane distillation.
Specifically, when the solid content is 30-50% by volume, discharging the concentrated solution containing crystals, separating crystals, drying, returning the concentrated solution to continue distillation, simultaneously adding fresh distillate to be distilled, continuing the process until no fresh distillate to be distilled exists any more, and finishing membrane distillation.
By adopting the technical scheme, the membrane distillation technology is carried out under normal pressure, the equipment is simple, the operation is convenient, the membrane distillation component is easy to design into a latent heat recovery mode, and the flexibility of forming a large-scale production system by efficient small-sized membrane components is realized; the solution does not need to be heated to the boiling point in the distillation process, the process can be carried out as long as the proper temperature difference is maintained on the two sides of the membrane, and the energy consumption is low.
In one embodiment, the crystallization is evaporative crystallization.
Preferably, the conditions for evaporative crystallization are normal pressure and the evaporation temperature is 80-100 ℃.
Evaporative crystallization is at an end when the solids content is 30-50wt% of the combined solution.
Preferably, before membrane distillation, hydrogen bromide solution is added to adjust the pH value of the combined solution to 6-7.
By adopting the technical scheme, the mixed solution is alkaline, the pH of the mixed solution from which the alcohol is separated is adjusted, the reverse proceeding of the hydrolysis process is avoided, meanwhile, the adjustment of the pH reduces the content of sodium hydroxide impurities in the sodium bromide product, and the purity of the sodium bromide product is improved.
The pH is adjusted by adopting the hydrogen bromide, so that new impurity ions are prevented from being introduced, and the purity of the sodium bromide product is improved.
In summary, the present application includes at least one of the following beneficial technical effects:
1. for the hazardous wastes containing bromoalkanes, a resource treatment mode is adopted, bromine resources in the wastes are recovered in a sodium bromide mode, and alcohol is obtained at the same time, so that the reduction and the resource of waste disposal are realized, the corrosion of bromine-containing wastes to equipment can be greatly reduced, the service life of the equipment is prolonged, and the service life is prolonged;
2. the method adopts the step-by-step bromine recovery, has good treatment effect and high bromine recovery rate which can reach more than 95 percent;
3. the recovered sodium bromide product has high purity, meets the first-class requirement of industrial sodium bromide HGT3809-2006, can be sold or sent to a manufacturer for recycling, and has good economic benefit.
Drawings
FIG. 1 is a schematic flow chart of the method of example 1.
Detailed Description
The present application is described in further detail in conjunction with the following.
Hazardous waste, namely rectification residue/liquid of a bromine manufacturer, wherein the manufacturer uses hydrogen bromide and propylene to prepare a bromopropane product, the hazardous waste is bromopropane rectification residue/liquid generated during bromopropane rectification, the hazardous waste mainly comprises bromopropane and contains 47wt% of bromine (calculated according to the mass of bromine atoms), and the specific detection result comprises 45wt% of organic bromine and 2wt% of inorganic bromine;
activated carbon, R50 honeycomb activated carbon, was manufactured by daqian purification materials ltd, engorgement city;
copper oxide, CUCAT catalyst, the manufacturer is Shanghai Xuan New Material science and technology Limited;
copper oxide, HZSM5-CUO, Zuoran environmental protection science and technology (Dalian) Co., Ltd was loaded on a molecular sieve;
molecular sieves, HZSM5, zuran environmental protection technologies (da lian) ltd;
alumina, AL, new materials of silicoaluminophosphate, santonin, inc.
Example 1
Referring to fig. 1, a resource recovery method for hazardous waste containing brominated alkanes comprises the following steps:
alkali washing: to 100kg of hazardous waste (distillation residue/liquid), 20kg of 5wt% aqueous sodium hydroxide solution was added under normal temperature conditions, at which time the ratio of sodium hydroxide: inorganic bromide = 1: 1 (molar ratio), stirring for 30 min; standing for 60 min; separating liquid, wherein the upper layer is alkaline solution, and the lower layer is bromine-containing waste liquid.
Hydrolysis: the bromine-containing waste liquid was fed into a hydrolysis reactor, and 75kg of a 30wt% sodium hydroxide solution was added thereto, at which time: organic bromine = 1: 1.1 (molar ratio), adding a catalyst of 5wt% of bromine-containing waste liquid, wherein the catalyst is copper oxide, reacting at 150 ℃ and 1Mpa until the reaction temperature is close to 7, and hydrolyzing for 4 hours until the hydrolysis is balanced.
Separation: standing for 60min, separating to obtain upper layer solution containing sodium bromide and alcohol solution (which are mutually soluble), which is mixed solution, and burning the insoluble residue/residual liquid in the lower layer.
Separating out alcohol: and (3) delivering the mixed solution to pervaporation equipment for pervaporation, wherein the pressure of the rear side of the membrane is 0.06mpa, the temperature of the front side of the membrane is 80 ℃, until no condensate is continuously generated on the rear side of the membrane, the pervaporation is terminated, a salt solution is obtained on the front side of the membrane, and the separated alcohol is obtained on the rear side of the membrane.
Neutralizing: the salt solution and the alkaline solution are combined to obtain a combined solution, the combined solution is sent to an acid-base adjusting device, 23kg of 20% hydrobromic acid solution with concentration is added to obtain a neutralization solution with pH 7, and the main component of the neutralization solution is sodium bromide.
Adsorbing, adding activated carbon in the neutralized mixed solution, and mixing uniformly, wherein the added amount of activated carbon is 0.3% of the mass of the mixed solution, the time is 60min, and the temperature is 25 ℃.
And (3) crystallization: and then filtering out active carbon in the neutralized solution, sending the filtered neutralized solution to membrane distillation equipment for membrane distillation crystallization, discharging a concentrated solution containing crystals when one side of the neutralized solution is a warm side, the warm side is 60 ℃, the cold side is 20 ℃, and the solid content of the neutralized solution is 50% by volume, separating out the crystals, drying, returning the solution to continue distillation, simultaneously adding fresh to-be-distilled liquid, and continuing the process until no fresh to-be-distilled liquid exists any more, so that 66kg of white crystals are obtained.
Example 2
The difference from example 1 is that: the hydrolysis process is carried out at normal pressure, i.e. 0.1 MPa.
19kg of a 20% strength hydrogen bromide solution were added to give a neutralized solution having a pH of 7.
63kg of white crystals were obtained.
Example 3
The difference from example 1 is that: no activated carbon was added for adsorption.
66.2kg of white crystals were obtained.
Example 4
The difference from example 1 is that: the temperature of the activated carbon adsorption was 20 ℃.
66kg of white crystals were obtained.
Example 5
The difference from example 1 is that: the temperature of the charcoal adsorption was 40 ℃.
68.78kg of white crystals were obtained.
Example 6
The difference from example 1 is that: no hydrogen bromide solution was added, at which point a solution of pH 8 was obtained.
62.6kg of white crystals were obtained.
Example 7
The difference from example 1 is that: 25kg of a 20% strength hydrogen bromide solution were added to obtain a neutralized solution having a pH of 5.
65kg of white crystals were obtained.
Example 8
The difference from example 1 is that: the catalyst is molecular sieve loaded copper oxide.
The time for hydrolysis to reach equilibrium was 4.3 h.
Example 9
The difference from example 1 is that: the catalyst is alumina.
The time for hydrolysis to reach equilibrium was 4.6 h.
Example 10
The difference from example 1 is that: the catalyst is a molecular sieve.
The time for hydrolysis to reach equilibrium was 4.5 h.
Example 11
The difference from example 1 is that: the catalyst is 3wt% of bromine-containing waste liquid.
The time for hydrolysis to reach equilibrium was 4.4 h.
Example 12
The difference from example 1 is that: the catalyst is 9wt% of bromine-containing waste liquid.
The time for hydrolysis to reach equilibrium was 4 h.
Example 13
The difference from example 1 is that:
separating out alcohol: the mixed solution was sent to a distillation column for distillation under 90 ℃ until no condensed liquid was produced and the distillation was stopped.
24kg of a 20% strength hydrogen bromide solution were added to obtain a neutralized solution having a pH of 7.
65.93kg of white crystals were obtained.
Example 14
The difference from example 13 is that:
separating out alcohol: the distillation conditions were 97 ℃ until no condensed liquid was produced and the distillation was stopped.
23kg of a 20% strength hydrogen bromide solution were added to give a neutralized solution having a pH of 7.
65.96kg of white crystals were obtained.
Example 15
The difference from example 13 is that:
separating out alcohol: the distillation conditions were at 100 ℃ until no condensed liquid was produced and distillation was stopped.
24kg of a 20% strength hydrogen bromide solution were added to obtain a neutralized solution having a pH of 7.
65.94kg of white crystals were obtained.
Example 16
The difference from example 1 is that:
and (3) crystallization: the filtered neutralized solution was sent to a crystallization kettle for evaporative crystallization at 90 ℃ until the solid content was 50wt% of the combined solution, and the evaporative crystallization was stopped to obtain 65.99kg of white crystals.
Comparative example 1
The difference from example 1 is that: the hydrolysis step was carried out directly without an alkaline washing step.
15kg of a 20% strength hydrogen bromide solution were added to obtain a neutralized solution having a pH of 7.
58.82kg of white crystals were obtained.
Comparative example 2
The difference from example 1 is that: firstly, the pH of the mixed solution is adjusted, 16kg of 20 percent hydrogen bromide solution is added to obtain a neutralized solution with the pH of 7, and then alcohol is separated out by pervaporation.
59.41kg of white crystals were obtained.
Performance detection
The following tests were carried out on the products obtained in examples 1 to 16 and comparative examples 1 to 2:
the sodium bromide product obtained was examined for sodium bromide mass (%), water (%), chloride (as Cl), and sulfate (as SO) with reference to HG/T3809-2006, Industrial sodium bromide4Calculated) mass fraction (%), bromate (in BrO)3Meter) mass fraction (%), iodide (in I) mass fraction (%), heavy metal (in Pb) mass fraction (%), iron (Fe) mass fraction (%), pH (50 g/ml solution); the yield of the sodium bromide is calculated,
yield = (w)1×77.67%）/(w2×47%+C×m×98.76%)×100%
Wherein, w1Is the quality of sodium bromide product, w1= mass of white crystal obtained × mass fraction of sodium bromide, 77.67% is mass ratio of bromine element in sodium bromide;
w2the mass of the hazardous waste is 100kg, and 47 percent of the mass of bromine in the hazardous waste is the percentage;
c (%) is the mass concentration of hydrogen bromide, and m is the addition amount of the hydrogen bromide solution;
the results of the sodium bromide product measurements and the sodium bromide yields are reported in table 1. Among these, the sodium bromide obtained in examples 8 to 12 was substantially identical to the sodium bromide obtained in example 1 in terms of NaBr mass fraction, moisture/%, yield and the like, and is not described in detail in table 1.
TABLE 1 Performance test results for sodium bromide
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Mass fraction/% of NaBr | 98.70 | 98.70 | 95.80 | 98.66 | 96.10 |
| Water content/%) | 0.4 | 0.2 | 0.3 | 0.4 | 0.5 |
| Mass fraction of chloride/% | 0.2 | 0.1 | 0.2 | 0.2 | 0.2 |
| Mass fraction of sulfate/%) | 0.01 | 0.02 | 0.02 | 0.01 | 0.01 |
| Bromate mass fraction/% | 0.001 | 0.002 | 0.002 | 0.001 | 0.001 |
| Mass fraction of iodide/%) | ND | ND | ND | ND | ND |
| Heavy metal (Pb) mass fraction/%) | ND | ND | ND | ND | ND |
| Iron mass fraction/% | ND | ND | ND | ND | ND |
| pH value | 7 | 7 | 7 | 7 | 7 |
| Yield/% | 98.16 | 95.16 | 95.57 | 98.12 | 98.15 |
| Example 6 | Example 7 | Comparative example 1 | Comparative example 2 | |
| Mass fraction/% of NaBr | 94.2 | 98.6 | 98.6 | 98.4 |
| Water content/%) | 0.3 | 0.4 | 0.3 | 0.5 |
| Mass fraction of chloride/% | 0.1 | 0.1 | 0.1 | 0.2 |
| Mass fraction of sulfate/%) | 0.01 | 0.01 | 0.02 | 0.01 |
| Bromate mass fraction/% | 0.001 | 0.002 | 0.001 | 0.001 |
| Mass fraction of iodide/%) | ND | ND | ND | ND |
| Heavy metal (Pb) mass fraction/%) | ND | ND | ND | ND |
| Iron mass fraction/% | ND | ND | ND | ND |
| pH value | 7 | 5 | 7 | 7 |
| Yield/% | 97.45 | 95.48 | 90.16 | 90.52 |
| Example 13 | Example 14 | Example 15 | Example 16 | |
| Mass fraction/% of NaBr | 98.51 | 98.62 | 98.48 | 98.68 |
| Water content/%) | 0.3 | 0.2 | 0.2 | 0.3 |
| Mass fraction of chloride/% | 0.1 | 0.2 | 0.1 | 0.2 |
| Mass fraction of sulfate/%) | 0.02 | 0.01 | 0.02 | 0.01 |
| Bromate mass fraction/% | 0.001 | 0.001 | 0.002 | 0.001 |
| Mass fraction of iodide/%) | ND | ND | ND | ND |
| Heavy metal (Pb) mass fraction/%) | ND | ND | ND | ND |
| Iron mass fraction/% | ND | ND | ND | ND |
| pH value | 7 | 7 | 7 | 7 |
| Yield/% | 97.50 | 98.02 | 97.48 | 98.13 |
Wherein ND is lower than the detection limit and is not detected.
As can be seen from table 1, the hydrolysis process pressure is different between example 1 and example 2, and the yield of sodium bromide is significantly higher in example 1 than in example 2 because the hydrolysis conversion rate is increased and the yield of sodium bromide is increased under the pressure of example 1.
In example 1, compared with example 3, in example 3, no activated carbon adsorption was performed, and the purity of sodium bromide obtained in example 1 was higher than that of example 3, because impurities such as residual organic substances can be adsorbed under the activated carbon adsorption conditions defined in the present application, and the purity of sodium bromide was improved.
In example 1, the temperature at which activated carbon is adsorbed is different from that in examples 4 to 5, and the purity of sodium bromide obtained in example 1 is higher.
In example 1, the pH of the combined solution was adjusted to be different from that of examples 6 to 7, and the purity of sodium bromide obtained in example 6 was lower and the yield of sodium bromide was lower in example 7 than that obtained in example 1.
Example 1 compared to comparative example 1, where no alkaline washing step was performed, the sodium bromide product yield of example 1 was higher.
Example 1 in comparison to comparative example 2, where the alcohol was separated by pervaporation after adjusting the pH, the sodium bromide product of example 1 was obtained in higher yield.
In examples 1 and 8-10, the hydrolysis rate was fastest in example 1, which was different from the catalyst selected; the catalysts were added in different amounts in examples 1 and 11-12, with the hydrolysis rates of examples 1 and 12 being the fastest.
Example 1 differs from examples 13-15 in the way the alcohol is separated, and examples 13-15 give sodium bromide in slightly lower yield than example 1, but the purity of the sodium bromide is similar, so the pervaporation process is superior. In examples 13 to 15, the yield of sodium bromide obtained in example 14 was the highest, and therefore the distillation conditions in example 14 were more preferable.
Compared with the example 16, the crystallization mode is different, but the yield and the purity of the obtained sodium bromide are basically similar, but the membrane distillation technology is carried out under normal pressure, the equipment is simple, the operation is convenient, the membrane distillation component is easy to design into a latent heat recovery mode, and the flexibility of constructing a large-scale production system by using efficient small-sized membrane components is realized; the solution does not need to be heated to the boiling point in the distillation process, the process can be carried out as long as the proper temperature difference is maintained on the two sides of the membrane, and the energy consumption is low.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. A resource recovery method for hazardous waste containing brominated alkanes is characterized by comprising the following steps: the method comprises the following steps:
s1: alkali washing, namely adding alkali liquor into the dangerous waste to wash and absorb, and separating liquid to obtain alkali washing liquid and bromine-containing waste liquid;
s2: hydrolyzing, namely mixing the bromine-containing waste liquid with a sodium hydroxide solution and a catalyst, hydrolyzing, and separating liquid to obtain a mixed solution;
s3: separating alcohol from the mixed solution to obtain a salt solution, and combining the alkaline washing solution and the salt solution to obtain a combined solution;
s4: crystallizing the combined solution, filtering, drying and crystallizing to obtain sodium bromide.
2. The resource recovery method of hazardous waste containing brominated alkanes according to claim 1, characterized in that: and the alkali liquor in the alkali washing step is sodium hydroxide aqueous solution.
3. The resource recovery method of hazardous waste containing brominated alkanes according to claim 1, characterized in that: during alkaline washing, the molar ratio of sodium hydroxide to inorganic bromide ions is (1-2): 1.
4. the resource recovery method of hazardous waste containing brominated alkanes according to claim 1, characterized in that: in the hydrolysis, the molar ratio of the sodium hydroxide to the organic bromine is (1-1.2): 1.
5. the resource recovery method of hazardous waste containing brominated alkanes according to claim 1, characterized in that: the hydrolysis conditions are as follows: the temperature is 100 ℃ and 150 ℃, and the pressure is 0.1-1 Mpa.
6. The resource recovery method of hazardous waste containing brominated alkanes according to claim 1, characterized in that: the catalyst is one or more of a molecular sieve, alumina, copper oxide and molecular sieve loaded copper oxide.
7. The resource recovery method of hazardous waste containing brominated alkanes according to claim 1, characterized in that: the dosage of the catalyst is 4-8wt% of bromine-containing waste liquid.
8. The resource recovery method of hazardous waste containing brominated alkanes according to claim 1, characterized in that: and adding active carbon into the combined solution for adsorption, wherein the adding amount of the active carbon in the combined solution is 0.1-0.5 wt% of the combined solution.
9. The resource recovery method of hazardous waste containing brominated alkanes according to claim 8, characterized in that: the temperature of the activated carbon adsorption is 20-40 ℃.
10. The resource recovery method of hazardous waste containing brominated alkanes according to claim 1, characterized in that: and before membrane distillation of the combined solution, adding a hydrogen bromide solution to adjust the pH to 6-7.
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