CN111548532A - Biomass intumescent flame retardant, preparation method and special device thereof - Google Patents
Biomass intumescent flame retardant, preparation method and special device thereof Download PDFInfo
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
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- C08K2003/323—Ammonium polyphosphate
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a biomass intumescent flame retardant, a preparation method and a special device thereof, belonging to the technical field of preparation of flame retardants. The flame retardant is a core-shell structure taking ammonium polyphosphate as a core and aminated lignin as a shell, wherein the aminated lignin is a cross-linking structure which is based on phenolated lignin and is connected with melamine on the carbon at the ortho position of phenolic hydroxyl of the phenolated lignin. The preparation method comprises the steps of firstly carrying out phenolization modification on lignin, then carrying out Mannich reaction on the phenolized lignin, melamine and formaldehyde to obtain phenolized-aminated lignin, and then reacting the phenolized-aminated lignin with ammonium polyphosphate to obtain the flame retardant. The special device adopts a two-stage control system, which comprises a lignin purification system, a lignin phenolization system, a mixture preparation system, a flame retardant synthesis system, and respective controllers and a master controller. The invention converts the lignin into the intumescent flame retardant with high economic benefit, and has the advantages of easily obtained raw materials, safe operation and easy reaction.
Description
Technical Field
The invention belongs to the technical field of preparation of flame retardants, and particularly relates to a biomass intumescent flame retardant, a preparation method thereof and a special device.
Background
Most of the fire retardants used in China at present are halogen fire retardants, but the halogen fire retardants can emit hydrogen halide gas and are accompanied with dense smoke under the conditions of high temperature and open fire. According to the survey: human asphyxiation due to hydrogen halide gas generated by halogen combustion is the most direct factor of injury and death in building fires. Moreover, most of the halogen flame retardants (especially polybromophenyl ether) can be decomposed to generate extractable organic compounds (EOX), and the compounds can be enriched in human bodies in various ways, so that the compounds have great harm to the health of the human bodies. Therefore, the development of a halogen-free flame retardant having environmental protection and high efficiency is urgently needed.
The lignin is one of the most abundant natural polymers in nature, the actual application of the lignin is very little, and the flame retardant serving as a high-added-value product of the lignin has wide application prospect. Chinese patent 2011100078002, published as 7-18/2012, discloses a method for preparing a biomass-based flame retardant, which comprises: (1) performing a first contact reaction on a straw lignin material, polyhydric alcohol and an acid catalyst for 1-4 hours at 100-135 ℃, and then adding starch to perform a second contact reaction to obtain a lignin modified substance; (2) and (2) carrying out a third contact reaction on phosphoric acid and pentaerythritol for 0.5-5 h at 100-180 ℃, adding polyether polyol, ammonium polyphosphate and melamine into a product obtained by the third contact reaction, and carrying out a fourth contact reaction for 0.5-4 h at 100-180 ℃ to obtain the flame retardant. The flame retardant can bring certain flame retardant performance to a substrate, but can be only applied to polyurethane foam, and has large limitation.
Revada (molecular construction of intumescent flame retardant and research on flame-retardant polylactic acid thereof [ D ]. Harbin Industrial university.2018.) in the paper mentions a method for flame-retardant treatment of polylactic acid, wherein melamine is used for modifying lignin by using Mannich reaction, and then the modified lignin is compounded and mixed with ammonium polyphosphate, and the mixture and the polylactic acid are subjected to melt blending to obtain the flame-retardant polylactic acid material. Liuyun and the like (research on MCA synergistic intumescent flame retardant LDPE foam [ J ] modern plastic processing application 2016,28(4):19-22.) are prepared from low-density polyethylene foam by a blending plastication-hot pressing method, wherein lignin is used as a carbon source, ammonium polyphosphate is used as an acid source and a gas source, melamine urate is used as a synergistic flame retardant, and low-density polyethylene is used as a base material. Although the application range of the lignin-based flame retardant is expanded in the prior art, the ammonium polyphosphate has the defects of poor compatibility with a polymer matrix, poor water resistance, easy agglomeration and the like, so that the ammonium polyphosphate is very easy to separate out and lose in practical application, and each component with the flame retardant effect is physically blended and added, so that temporary proportioning is needed during use, the operation difficulty is increased, in addition, as an additive flame retardant, each component is only physically blended and is easy to migrate, the flame retardant performance and the mechanical performance of the material are rapidly reduced, and the application of the whole intumescent flame retardant system in occasions with higher flame retardant performance requirements is greatly limited.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a biomass intumescent flame retardant, another object of the present invention is directed to a preparation method of the flame retardant, and a special device for the preparation method.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the biomass intumescent flame retardant is a core-shell structure taking ammonium polyphosphate as a core and aminated lignin as a shell, wherein the aminated lignin is a cross-linking structure taking phenolated lignin as a base and connecting melamine on carbon at the ortho position of phenolic hydroxyl of the phenolated lignin.
A preparation method of a biomass intumescent flame retardant comprises the steps of carrying out phenolization modification on lignin to obtain phenolized lignin, carrying out Mannich reaction on the phenolized lignin, melamine and formaldehyde to obtain phenolized-aminated lignin, and then reacting the phenolized-aminated lignin with ammonium polyphosphate to obtain the biomass intumescent flame retardant.
The specific reaction steps are as follows:
step 1, mixing lignin and a sulfuric acid solution, stirring for 1-2 hours at 75-85 ℃, then raising the temperature to 90-100 ℃, adding phenol, stirring for 1-2 hours, cooling, washing and drying to obtain phenolated lignin;
step 2, mixing and stirring ammonium polyphosphate and an ethanol aqueous solution for 30-60 min, then adding melamine, heating to 65-75 ℃, stirring for 5.5-6.5 h, cooling, washing and drying to obtain a mixture of melamine and ammonium polyphosphate;
and 3, dispersing a mixture of phenolated lignin, melamine and ammonium polyphosphate into N, N-dimethylformamide, heating and stirring, adding a formaldehyde solution when heating to 70-80 ℃, reacting for 2.5-3.5 h, cooling, washing and drying to obtain the biomass intumescent flame retardant.
Preferably, the mass ratio of the ammonium polyphosphate to the melamine is (1-1.4): 1.
Preferably, the mass ratio of the phenolated lignin to the mixture of melamine and ammonium polyphosphate is 1 (4-6).
Preferably, the mass ratio of the phenolated lignin to the formaldehyde is 1 (0.6-0.8).
Preferably, the lignin is enzymatic lignin.
Preferably, in the step 1, the concentration of the sulfuric acid solution is 1.5-2.5 mol/L.
Preferably, in the step 2, the volume ratio of the ethanol to the water in the ethanol aqueous solution is (2-3): 1.
A special device for the preparation method, which comprises a lignin purification system, a lignin phenolization system, a mixture preparation system and a flame retardant synthesis system,
in the lignin purification system, discharge ports of an enzymatic hydrolysis lignin storage tank and a sodium hydroxide solution storage tank are connected with a first reactor, a discharge port of the first reactor is connected with a first filter, discharge ports of a hydrochloric acid storage tank, a distilled water storage tank and the first reactor are connected with a pH adjusting tank, a discharge port of the pH adjusting tank is respectively connected with a first waste storage tank and a first drying tank, and a discharge port of the first drying tank is connected with a second reactor;
in the lignin phenolization system, discharge ports of a sulfuric acid storage tank and a phenol storage tank are connected with a second reactor, discharge ports of the second reactor and an ether storage tank are connected with a second flushing device, an ether recovery device is respectively connected with the second flushing device and a second dryer, a discharge port of the second flushing device is connected with a second dryer, and a discharge port of the second dryer is connected with a third reactor;
in the mixture preparation system, discharge ports of a melamine storage tank and an ammonium polyphosphate storage tank are connected with a fourth reactor, a discharge port of an ethanol water solution storage tank is respectively connected with the fourth reactor and a fourth flushing device, a discharge port of the fourth reactor is connected with the fourth flushing device, a discharge port of the fourth flushing device is connected with a fourth filter, a discharge port of the fourth filter is connected with a fourth dryer, a feed port of an ethanol recovery tank is connected with the fourth dryer, a discharge port of the fourth dryer is connected with the fourth filter, and a discharge port of the fourth dryer is connected with a third reactor;
in the fire retardant synthesis system, the discharge gate of solvent storage jar, formaldehyde storage jar, distilled water storage jar links to each other with the third reactor, and the discharge gate of third reactor links to each other with the third filter, and the discharge gate of third filter links to each other with the third desicator, and the discharge gate of third desicator links to each other with fire retardant storage jar.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the invention converts the lignin into the intumescent flame retardant with high economic benefit, and has the advantages of easily obtained raw materials, safe operation and easy reaction. The obtained flame retardant is of a core-shell structure, the external capsule material has the effects of isolating and protecting the internal ammonium polyphosphate, the defects of the ammonium polyphosphate are overcome, and when the flame retardant is applied to epoxy resin, the flame retardant property and the water resistance of the material are greatly improved.
The special intelligent equipment has a compact structure, adopts a two-stage control system, is favorable for realizing accurate control of the reaction process, can realize the switching between stirring and reflux stirring due to the electromagnetic valve in the stirring equipment, is favorable for reaction, can recycle the waste materials stored in the waste material storage tank after further recovery, and is suitable for industrial popularization and application.
Drawings
FIG. 1 is a schematic process flow diagram of a flame retardant of the present invention;
FIG. 2 is a schematic structural view of a flame retardant of the present invention;
FIG. 3(a) is an X-ray photoelectron spectrum of melamine, and FIG. 3(b) is an X-ray photoelectron spectrum of the intumescent flame retardant obtained in example 1;
FIG. 4(a) is a picture of the morphology of ammonium polyphosphate, and FIG. 4(b) is a picture of the morphology of the intumescent flame retardant obtained in example 1;
FIG. 5 is a schematic view of a special apparatus for preparing the flame retardant of the present invention;
in fig. 5: 11. an enzymolysis lignin storage tank; 12. a sodium hydroxide solution storage tank; 13. a first reactor; 14. a hydrochloric acid storage tank; 15. a first filter; 16. a distilled water storage tank; 17. a pH adjusting tank; 18. a first waste storage tank; 19. a first drying tank; 21. a sulfuric acid storage tank; 22. a phenol storage tank; 23. a second reactor; 24. ether storage tank; 25. a second flushing device; 26. an ether recovery device; 27. a second dryer; 31. a solvent storage tank; 32. a formaldehyde storage tank; 33. a distilled water storage tank; 34. a third reactor; 35. a third filter; 36. a third dryer; 37. a fire retardant storage tank; 41. a melamine storage tank; 42. an ammonium polyphosphate storage tank; 43. an ethanol water solution storage tank; 44. a fourth reactor; 45. a fourth flushing device; 46. a fourth filter: 47. an ethanol recovery tank; 48. a fourth dryer; c1, a first controller; c2, a second controller; c3, a third controller; c4, a fourth controller; c0, and a general controller.
Detailed Description
The invention is further described with reference to specific examples.
The following examples were prepared from the following raw materials:
the enzymatic hydrolysis lignin is purchased from Lingyu chemical industry Co., Ltd, Jinzhou, and the lignin content is 70-80%;
epoxy resin was purchased from Nantong star plastics, Inc. under the brand number E51;
the rest raw materials are all in commercial analytical purity.
The adopted test instrument is as follows:
XPS analysis adopts an X-ray photoelectron spectrometer with the model number AXIS Ultra DLD;
the surface morphology analysis of the material adopts a Japanese JSM-7600F field emission electron microscope;
thermogravimetric analysis was carried out using a Japanese Shimadzu DTG-60AH type thermogravimetric analyzer;
the flame retardant performance test adopts an HC-2 oxygen index instrument;
the combustion performance test was carried out using an FTT2000 cone calorimeter from FTT, UK.
Example 1
A preparation method of a biomass intumescent flame retardant is disclosed, referring to FIG. 1, and comprises the following steps:
(1) purification of lignin
Mixing 20g of enzymatic hydrolysis lignin with 200mL of 10 wt% sodium hydroxide solution, heating to 75 ℃, fully stirring for 1h, filtering to remove undissolved precipitate, dropwise adding 10% vol hydrochloric acid into the obtained solution to adjust the pH value to 3.0-4.0 so as to completely precipitate the lignin, and washing the precipitate for 3 times by using distilled water until the washing water becomes neutral. The washed lignin was dried at 80 ℃ under reduced pressure until no weight change was observed and the product was labeled as Lig-O.
(2) Phenolization modification of lignin
10g of Lig-O was mixed with 70mL of H2SO4The solutions (2mol/L) were mixed and then stirred at 80 ℃ for 1.5 h. After stirring was complete, the temperature was raised to 95 ℃ and 18 was addedg phenol, and stirred for a further 1.5 h. After the reaction was complete, the solution was cooled to room temperature, washed 3 times with diethyl ether and distilled water, and the resulting modification was dried to constant weight, and the product was labeled Lig-pH.
(3) Preparation of ammonium polyphosphate and melamine mixture
1L of ethanol aqueous solution (Vethanol: Vwater: 5:2) was prepared for later use. 6g of ammonium polyphosphate (APP) and 140mL of ethanol aqueous solution are mixed and added into a stirrer, and stirred for 30min at normal temperature. After the ammonium polyphosphate had dispersed, 5g of Melamine (MEL) were added and the temperature was raised to 70 ℃ and stirred under reflux for 6 h. After stirring, the solution was cooled to room temperature, 500mL of ethanol solution was added, the solid was washed repeatedly 3 times, filtered, and the washed solid was dried in a vacuum oven at 70 ℃ for 12 hours.
(4) Synthesis of intumescent flame retardant
4g of phenolated lignin (Lig-pH) and 20g of a mixture of melamine and ammonium polyphosphate were added to the reactor, and 100mL of N, N-Dimethylformamide (DMF) were added, and placed in an oil bath pan and heated with stirring. When the temperature reaches 75 ℃, 7.5g of formaldehyde solution (mass fraction is 40%) is added, and the Mannich reaction is carried out after stirring and refluxing for 3 hours. After the reaction was completed, the solution was cooled to room temperature, 500mL of distilled water was added, stirred for 5 minutes and then filtered. And (3) drying the obtained solid in a vacuum drying oven at 70 ℃ for 24h to obtain the biomass intumescent flame retardant with the yield of 54.5%.
The elemental composition and valence of the prepared flame retardant were analyzed, see fig. 3. Wherein, fig. 3(a) is an X-ray photoelectron spectrum of melamine, and fig. 3(b) is an X-ray photoelectron spectrum of the obtained intumescent flame retardant. The peak at 401.2eV in the graph is NH in APP4 +The peaks indicate that after the mannich reaction, phenolated-aminated lignin may coat APP.
And carrying out gold spraying treatment on the sample to improve the conductivity of the sample. The appearance of the ammonium polyphosphate and the surface of the prepared flame retardant are observed by adopting a field emission electron microscope with the accelerating voltage of 15kV, which is shown in figure 4. Wherein, fig. 4(a) is a picture of the shape of ammonium polyphosphate, fig. 4(b) is a picture of the shape of the obtained intumescent flame retardant, and it can be seen from the picture that APP is a columnar structure with the size of about 10um and has a smooth surface. After the mannich reaction, the particle size in the figure is about 10um, which can be concluded to be APP, but the surface has become rough, with many small particles attached, indicating that after the mannich reaction, phenolated-aminated lignin coats APP without changing the shape of APP.
By combining the morphology graph and the spectrum of XPS, the successful coating of APP by the phenolated-aminated lignin after the Mannich reaction can be proved to be a core-shell structure. The schematic structure of the flame retardant is shown in FIG. 2.
The thermal weight loss analysis is carried out on the flame retardant, protective gas and purge gas are nitrogen, the flow rate of air flow is 50mL/min, the heating rate is 15 ℃/min, the temperature of the maximum decomposition rate is 382 ℃, and the carbon residue rate at 800 ℃ is 37.5%.
When the additive amount is 10%, the following components are added:
the UL-94 vertical burning test is passed, and the test grade reaches V-0 grade;
the sample bar size is 100mm multiplied by 6.5mm multiplied by 3.2mm, and the limit oxygen index of the sample bar is measured to be 36.1 percent according to the ATSM D2863 standard;
the specimens having a size of 100mm × 100mm × 3.2.2 mm were tested by placing them on a cone calorimeter in accordance with ISO 5660-1 standard, each specimen being wrapped in aluminum foil and having a heat flux of 50kW/m2Total smoke release of 9.9m2/m2The total heat release amount is 53.1MJ/m2。
And (3) placing a sample strip with the thickness of 3.2mm into a constant-temperature water bath at 70 ℃, taking out after 168 hours, drying for 3 hours at 120 ℃, cooling to room temperature, and testing the flame retardant property, wherein the vertical combustion test grade is still V-0 grade, and the limiting oxygen index is 33.7%.
Example 2
A preparation method of a biomass intumescent flame retardant is disclosed, referring to FIG. 1, and comprises the following steps:
(1) purification of lignin
Mixing 20g of enzymatic hydrolysis lignin with 200mL of 10 wt% sodium hydroxide solution, heating to 70 ℃, fully stirring for 1.5h, filtering to remove undissolved precipitate, dropwise adding 10% vol hydrochloric acid into the obtained solution to adjust the pH value to 3.0-4.0 so as to completely precipitate the lignin, and washing the precipitate with distilled water for 5 times until the washing water becomes neutral. The product was dried at 75 ℃ under reduced pressure until there was no change in weight, labeled Lig-O.
(2) Phenolization modification of lignin
10g of Lig-O was mixed with 70mL of H2SO4The solutions (2mol/L) were mixed and then stirred at 75 ℃ for 2 h. After stirring was complete, the temperature was raised to 90 ℃ and 25g phenol was added and stirred for an additional 1.5 h. After the reaction was complete, the solution was cooled to room temperature, washed 3 times with diethyl ether and distilled water, and the resulting modification was dried to constant weight, labeled Lig-pH.
(3) Preparation of ammonium polyphosphate and melamine mixture
1L of an aqueous ethanol solution was prepared (Vethanol: Vwater: 5: 2). 6g of ammonium polyphosphate and 140mL of ethanol aqueous solution are mixed and added into a stirrer, and the mixture is stirred for 1 hour at normal temperature. After the ammonium polyphosphate had been dispersed, 4.5g of melamine were added, the temperature was raised to 65 ℃ and the mixture was stirred under reflux for 5.5 h. After stirring, the solution was cooled to room temperature, 500mL of ethanol solution was added, the solid was washed repeatedly 3 times, filtered, and the washed solid was dried in a vacuum oven at 75 ℃ for 10 hours.
(4) Synthesis of intumescent flame retardant
6g of phenolated lignin (Lig-pH) and 25g of a mixture of melamine and ammonium polyphosphate were added to the reactor, and 150mL of DMF was added, placed in an oil bath and heated with stirring. When the temperature reaches 80 ℃, 9g of formaldehyde solution (mass fraction: 40%) is added, and the mixture is stirred and refluxed for 2.5 hours. After the reaction was completed, the solution was cooled to room temperature, 500mL of distilled water was added, stirred for 5 minutes and then filtered. And repeating the steps for 3 times, and drying the obtained solid in a vacuum drying oven at 75 ℃ for 10 hours to obtain the biomass intumescent flame retardant with the yield of 52.3%.
The thermal weight loss analysis is carried out on the flame retardant, protective gas and purge gas are nitrogen, the flow rate of gas flow is 50mL/min, the heating rate is 15 ℃/min, the temperature of the maximum decomposition rate is 373 ℃, and the carbon residue rate at 800 ℃ is 36.1%.
When the additive amount is 13%, the following components are applied to epoxy resin:
the UL-94 vertical burning test is passed, and the test grade reaches V-0 grade;
the sample size is 100mm multiplied by 6.5mm multiplied by 3.2mm, and the limit oxygen index is 35.7 percent according to the ATSM D2863 standard;
the specimens having a size of 100mm × 100mm × 3.2.2 mm were tested by placing them on a cone calorimeter in accordance with ISO 5660-1 standard, each specimen being wrapped in aluminum foil and having a heat flux of 50kW/m2The total smoke release amount is 10.3m2/m2The total heat release amount is 54.2MJ/m2。
And (3) placing a sample strip with the thickness of 3.2mm into a constant-temperature water bath at 70 ℃, taking out after 168 hours, drying for 3 hours at 120 ℃, cooling to room temperature, and testing the flame retardant property, wherein the vertical combustion test grade is still V-0 grade, and the limiting oxygen index is 33.5%.
Example 3
The special intelligent device adopting the preparation method comprises a lignin purification system, a lignin phenolization system, an ammonium polyphosphate and melamine mixture preparation system, a flame retardant synthesis system, a first controller C1, a second controller C2, a third controller C3, a fourth controller C4 and a master controller C0 as shown in FIG. 5.
Wherein the lignin purification system comprises: the discharge ports of the enzymolysis lignin storage tank 11 and the sodium hydroxide solution storage tank 12 are connected with the first reactor 13, the discharge port of the first reactor 13 is connected with the first filter 15, the discharge ports of the hydrochloric acid storage tank 14, the distilled water storage tank 16 and the first reactor 15 are connected with the pH adjusting tank 17, the discharge port of the pH adjusting tank 17 is respectively connected with the first waste storage tank 18 and the first drying tank 19, and the discharge port of the first drying tank 19 is connected with the second reactor 23.
The lignin phenolization system comprises: the discharge ports of the sulfuric acid storage tank 21 and the phenol storage tank 22 are connected with the second reactor 23, the discharge ports of the second reactor 23 and the diethyl ether storage tank 24 are connected with the second flushing device 25, the diethyl ether recovery device 26 is respectively connected with the second flushing device 25 and the second dryer 27, the discharge port of the second flushing device 25 is connected with the second dryer 27, and the discharge port of the second dryer 27 is connected with the third reactor 34.
The ammonium polyphosphate and melamine mixture preparation system comprises: the melamine storage tank 41 and the ammonium polyphosphate storage tank 42 are connected with the fourth reactor 44, the ethanol water solution storage tank 43 is connected with the fourth reactor 44 and the fourth flushing device 45 respectively, the fourth reactor 44 is connected with the fourth flushing device 45, the fourth flushing device 45 is connected with the fourth filter 46, the fourth filter 46 is connected with the fourth dryer 48, the ethanol recovery tank 47 is connected with the fourth dryer 48 at the feed inlet, the fourth filter 46 is connected at the discharge outlet, and the fourth dryer 48 is connected with the third reactor 34 at the discharge outlet.
The flame retardant synthesis system comprises: the discharge ports of the DMF storage tank 31, the formaldehyde storage tank 32 and the distilled water storage tank 33 are connected with the third reactor 34, the discharge port of the third reactor 34 is connected with the third filter 35, the discharge port of the third filter 35 is connected with the third dryer 36, and the third dryer 36 is connected with the flame retardant storage tank 37.
The main reaction of this device goes on in each reactor, wherein the third reactor, the fourth reactor contains the pipeline of being connected by the solenoid valve, can realize stirring and the free switching of backward flow stirring, each reactor, the drying tank all contains temperature sensor and heating device, be favorable to realizing the control to the temperature, the pH adjusting tank, the flushing tank all contains the pH sensor, be favorable to realizing the control to pH, each connecting tube is controlled by the solenoid valve, be favorable to realizing the timing function, the pipeline solenoid valve of each system, the device links to each other with the controller that corresponds the system, each level controller links to each other with total controller, the operator only needs to operate total controller, the controller is the PLC controller.
The operation method of the device comprises the following steps:
pumping an enzymolysis lignin storage tank 11 and a sodium hydroxide solution storage tank 12 into a first reactor 13, heating to 75 ℃, fully stirring for 1h, pumping the products into a first filter 15, filtering for 15min, discharging the filtered products into a pH adjusting tank 17, pumping hydrochloric acid into the pH adjusting tank 17 by a hydrochloric acid storage tank 14, adjusting the pH to 3-4, discharging the liquid into a first waste storage tank 18, pumping distilled water into a distilled water storage tank 16, flushing the residual precipitate until the pH is neutral, discharging the liquid into the first waste storage tank 18, conveying the solid into a first drying tank 19, drying at 80 ℃ for 30min, conveying the solid into a second reactor 23, pumping sulfuric acid from a sulfuric acid storage tank 21 into a second reactor 23, stirring for 1.5h at 80 ℃, heating to 95 ℃ after stirring, and then allowing phenol in a phenol storage tank 22 to flow into the second reactor 23, stirring for 1.5h, discharging the product into a second washing device 25, extracting diethyl ether from a diethyl ether storage tank 24 and a diethyl ether recovery device 26, washing for 30min, discharging the solution into a second dryer 27 after the completion, recovering the liquid into the diethyl ether recovery device 26, and conveying the solid into a third reactor 34.
Discharging the liquid in the ammonium polyphosphate storage tank 42 and the ethanol water solution storage tank 43 into a fourth reactor 44, stirring at normal temperature for 30min, then discharging the melamine storage tank 41 into the fourth reactor 44, raising the temperature to 70 ℃, opening an electromagnetic valve, carrying out reflux stirring for 6h, discharging the product into a fourth flushing device 45 after stirring is finished, pumping the ethanol water solution from the ethanol water solution storage tank 43, flushing for 30min, simultaneously discharging the product into a fourth filter 46, filtering, discharging the liquid into an ethanol recovery tank 47, conveying the solid into a fourth dryer 48, drying for 12h at 70 ℃, discharging the evaporated liquid into the ethanol recovery tank 47, and conveying the solid into the third reactor 34.
Adding the solid in the second dryer 27 and the fourth dryer 48 and the solution in the DMF storage tank 31 into a third reactor 34, heating and stirring, extracting formaldehyde from a formaldehyde storage tank 32 when the temperature reaches 75 ℃ and adding the formaldehyde into the third reactor 34, opening an electromagnetic valve, carrying out reflux stirring for 3h, extracting distilled water from a distilled water storage tank 33 after the reaction is finished, continuing stirring for 5min, discharging the product to a third filter 35 after the reaction is finished, filtering for 15min, conveying the solid into a third dryer 36 after the filtration is finished, drying for 24h at 70 ℃, and conveying the dried solid into a flame retardant storage tank 37.
Claims (10)
1. The biomass intumescent flame retardant is characterized in that the biomass intumescent flame retardant is a core-shell structure taking ammonium polyphosphate as a core and aminated lignin as a shell, wherein the aminated lignin is a cross-linked structure based on phenolated lignin and formed by connecting melamine on carbon at the ortho-position of phenolic hydroxyl groups of the phenolated lignin.
2. The preparation method of the biomass intumescent flame retardant of claim 1, characterized in that lignin is phenolized and modified to obtain phenolized lignin, then phenolized lignin is subjected to Mannich reaction with melamine and formaldehyde to obtain phenolized-aminated lignin, and then phenolized-aminated lignin is reacted with ammonium polyphosphate to obtain the biomass intumescent flame retardant.
3. The preparation method of the biomass intumescent flame retardant of claim 2, characterized by comprising the following specific reaction steps:
step 1, mixing lignin and a sulfuric acid solution, stirring for 1-2 hours at 75-85 ℃, then raising the temperature to 90-100 ℃, adding phenol, stirring for 1-2 hours, cooling, washing and drying to obtain phenolated lignin;
step 2, mixing and stirring ammonium polyphosphate and an ethanol aqueous solution for 30-60 min, then adding melamine, heating to 65-75 ℃, stirring for 5.5-6.5 h, cooling, washing and drying to obtain a mixture of melamine and ammonium polyphosphate;
and 3, dispersing a mixture of phenolated lignin, melamine and ammonium polyphosphate into N, N-dimethylformamide, heating and stirring, adding a formaldehyde solution when heating to 70-80 ℃, reacting for 2.5-3.5 h, cooling, washing and drying to obtain the biomass intumescent flame retardant.
4. The preparation method of the biomass intumescent flame retardant of claim 2 or 3, characterized in that the mass ratio of ammonium polyphosphate to melamine is (1-1.4): 1.
5. The preparation method of the biomass intumescent flame retardant of claim 3, characterized in that the mass ratio of the phenolated lignin to the mixture of melamine and ammonium polyphosphate is 1 (4-6).
6. The preparation method of the biomass intumescent flame retardant of claim 2 or 3, wherein the mass ratio of the phenolated lignin to the formaldehyde is 1 (0.6-0.8).
7. The preparation method of the biomass intumescent flame retardant of claim 2 or 3, characterized in that the lignin is enzymatic lignin.
8. The preparation method of the biomass intumescent flame retardant of claim 3, wherein in the step 1, the concentration of the sulfuric acid solution is 1.5-2.5 mol/L.
9. The preparation method of the biomass intumescent flame retardant of claim 3, wherein in the step 2, the volume ratio of ethanol to water in the ethanol aqueous solution is (2-3): 1.
10. A special apparatus for the production method according to claim 2 to 9, comprising a lignin purification system, a lignin phenolization system, a mixture production system, and a flame retardant synthesis system,
in the lignin purification system, discharge ports of an enzymolysis lignin storage tank (11) and a sodium hydroxide solution storage tank (12) are connected with a first reactor (13), a discharge port of the first reactor (13) is connected with a first filter (15), discharge ports of a hydrochloric acid storage tank (14), a distilled water storage tank (16) and the first reactor (15) are connected with a pH adjusting tank (17), a discharge port of the pH adjusting tank (17) is respectively connected with a first waste storage tank (18) and a first drying tank (19), and a discharge port of the first drying tank (19) is connected with a second reactor (23);
in the lignin phenolization system, discharge ports of a sulfuric acid storage tank (21) and a phenol storage tank (22) are connected with a second reactor (23), discharge ports of the second reactor (23) and an ether storage tank (24) are connected with a second flushing device (25), an ether recovery device (26) is respectively connected with the second flushing device (25) and a second dryer (27), a discharge port of the second flushing device (25) is connected with the second dryer (27), and a discharge port of the second dryer (27) is connected with a third reactor (34);
in the mixture preparation system, discharge ports of a melamine storage tank (41) and an ammonium polyphosphate storage tank (42) are connected with a fourth reactor (44), a discharge port of an ethanol water solution storage tank (43) is respectively connected with the fourth reactor (44) and a fourth flushing device (45), a discharge port of the fourth reactor (44) is connected with the fourth flushing device (45), a discharge port of the fourth flushing device (45) is connected with a fourth filter (46), a discharge port of the fourth filter (46) is connected with a fourth dryer (48), a feed port of an ethanol recovery tank (47) is connected with the fourth dryer (48), a discharge port of the ethanol recovery tank is connected with the fourth filter (46), and a discharge port of the fourth dryer (48) is connected with a third reactor (34);
in the fire retardant synthesis system, the discharge ports of a solvent storage tank (31), a formaldehyde storage tank (32) and a distilled water storage tank (33) are connected with a third reactor (34), the discharge port of the third reactor (34) is connected with a third filter (35), the discharge port of the third filter (35) is connected with a third dryer (36), and the discharge port of the third dryer (36) is connected with a fire retardant storage tank (37).
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