CN108976503B - Method for co-production of rubber flame retardant by using phosphogypsum and fly ash to prepare acid - Google Patents
Method for co-production of rubber flame retardant by using phosphogypsum and fly ash to prepare acid Download PDFInfo
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Abstract
The invention provides a method for preparing acid and coproducing a rubber flame retardant by using phosphogypsum and fly ash, which comprises the following steps: mixing and grinding phosphogypsum, fly ash, additive and modifier to prepare raw material, feeding the raw material into a kiln for roasting to prepare clinker, carrying out water grinding on the clinker for dissolution, carrying out solid-liquid separation, processing the separated solid after roasting to prepare sulfuric acid, purifying the separated liquid, and introducing CO2Preparing aluminum hydroxide, and then preparing the aluminum hydroxide, isoprene rubber, fumed silica, chlorinated paraffin, hexabromocyclododecane, zinc borate, sodium molybdate, an anti-aging agent and a vulcanizing agent into the rubber flame retardant. The invention comprehensively utilizes the phosphogypsum and the fly ash, has simple process, high utilization rate and high added value, and the produced aluminum hydroxide is a good flame retardant additive raw material used as a rubber flame retardant, and the prepared rubber flame retardant has the characteristic of low production cost.
Description
Technical Field
The invention relates to a method for preparing acid and co-producing a rubber flame retardant by using phosphogypsum and fly ash, belonging to the field of metallurgical chemical industry.
Background
Phosphogypsum refers to solid waste residue generated when phosphorite is treated by sulfuric acid in phosphoric acid production, and the main component of the phosphogypsum is calcium sulfate and also contains various other impurities. At present, the total amount of the phosphogypsum discharged all over the world every year is about 1.2-1.4 hundred million tons, China is about 5000 million tons, and the total amount of the phosphogypsum discharged all over the world is 25-29 percent, the amount is on an increasing trend, the stacking amount of the phosphogypsum in China currently reaches 2.5 million tons, and the discharged phosphogypsum slag occupies a large amount of land, forms slag hills and seriously pollutes the environment.
Fly ash is fine ash collected from flue gas generated after coal combustion, and is main solid waste discharged from a coal-fired power plant. Along with the development of the power industry, the discharge amount of the fly ash of a coal-fired power plant is increased year by year, and the fly ash becomes one of industrial waste residues with larger discharge amount in China. At present, the annual output of fly ash in China exceeds 6 hundred million tons, which causes great pressure on national economic construction and ecological environment in China.
The rubber product not only provides indispensable daily and medical products for people, but also is increasingly used in the heavy industries such as traffic, mining industry, building industry, machinery, electronics and the like and the emerging industries. The performance requirements of different industries on rubber products are different, and the rubber used for the cable buffer layer needs to have good flame retardance so as to ensure the safety of the cable. The main component of the existing rubber flame retardant additive is almost aluminum hydroxide, but the market price of the existing aluminum hydroxide is high, so that the problem of high production cost of the rubber flame retardant is caused.
At present, on one hand, the phosphogypsum and the fly ash in China have the problems of large accumulation and environmental pollution, and on the other hand, the phosphogypsum and the fly ash also have a plurality of useful components, but at present, people mainly use the phosphogypsum and the fly ash in the aspect of building materials, but acid in the phosphogypsum can cause poor quality of the building materials, and the additional yield value of the utilization mode is low. At present, the process for preparing acid and co-producing rubber flame retardant by comprehensively utilizing phosphogypsum and fly ash is not reported.
Object of the Invention
The invention aims to provide a method for preparing acid and co-producing a rubber flame retardant by using phosphogypsum and fly ash. The invention comprehensively utilizes the phosphogypsum and the fly ash, has simple process, high utilization rate and high added value, and the produced aluminum hydroxide is a good flame retardant additive raw material used as a rubber flame retardant, and the prepared rubber flame retardant has the characteristic of low production cost.
Technical scheme of the invention
A method for preparing acid and coproducing rubber flame retardant from phosphogypsum and fly ash comprises the following steps:
A. mixing and grinding phosphogypsum, fly ash, an additive and a modifier to prepare raw materials, feeding the raw materials into a kiln for roasting to prepare clinker, carrying out water grinding on the clinker for dissolution, and carrying out solid-liquid separation;
B. b, carrying out flotation on the precipitate obtained by solid-liquid separation in the step A, separating out sulfide, roasting the separated sulfide, carrying out catalytic reaction on the flue gas generated by roasting through vanadium pentoxide, and absorbing the flue gas by adopting concentrated sulfuric acid to prepare sulfuric acid;
C. adding calcium oxide into the liquid obtained by solid-liquid separation in the step A, heating, stirring and filtering to prepare a sodium metaaluminate solution;
D. c, introducing CO into the sodium metaaluminate solution prepared in the step C2Until no precipitate is generated, washing the precipitate with distilled water, drying the washed precipitate, and grinding to obtain aluminum hydroxide;
E. and D, putting the aluminum hydroxide prepared in the step D into a mixing roll, adding fumed silica, chlorinated paraffin, hexabromocyclododecane, zinc borate, sodium molybdate and an anti-aging agent, and mixing to obtain the rubber flame retardant.
In the method for producing acid and co-producing rubber flame retardant by using phosphogypsum and fly ash, in the step A, the additive is sodium carbonate, sodium sulfate or caustic soda; the modifier is anthracite, carbon or coal gangue; the kiln is an industrial rotary kiln, an industrial tunnel kiln or an industrial vertical kiln.
In the step A, the phosphogypsum and the fly ash are mixed in the raw material according to the weight ratio of 1-1.4:1-1.7, and the additive is added according to the Na contained in the raw material2O and Al2O3+Fe2O3The total molecular ratio is 1:1, and the mixing ratio of the modifier is 12-28% of the total weight of the raw material; the roasting temperature is 1050-; the liquid-solid volume ratio during water milling dissolution is 3-8: 1.
In the method for co-producing the rubber flame retardant by using the phosphogypsum and the fly ash for preparing the acid, in the step B, the roasting temperature is 1150-1250 ℃; the time is 3-5 h; the condition is that the sulfide is put in 40-50% oxygen-rich environment.
In the method for co-producing the rubber flame retardant by using the phosphogypsum and the fly ash for preparing the acid, in the step C, the calcium oxide is analytically pure, and the using amount of the calcium oxide is 7-10 g/L; the heating temperature is 75-95 ℃; the stirring time is 1-2 h.
In the method for preparing acid and CO-producing rubber flame retardant by using phosphogypsum and fly ash, in step D, the CO is used2CO in gas2Is greater than 37%; the drying temperature is 95-105 ℃.
In the step E, the anti-aging agent is an anti-aging agent RD.
According to the method for co-producing the rubber flame retardant by the phosphogypsum and fly ash acid production, in the step E, the rubber flame retardant comprises 30-40 parts by weight of aluminum hydroxide, 30-40 parts by weight of fumed silica, 2-4 parts by weight of chlorinated paraffin, 3-5 parts by weight of hexabromocyclododecane, 3-5 parts by weight of zinc borate, 1-2 parts by weight of sodium molybdate and 1-3 parts by weight of an anti-aging agent.
According to the method for co-producing the rubber flame retardant by using the phosphogypsum and the fly ash to prepare the acid, the rubber flame retardant comprises 35 parts by weight of aluminum hydroxide, 35 parts by weight of fumed silica, 3 parts by weight of chlorinated paraffin, 4 parts by weight of hexabromocyclododecane, 4 parts by weight of zinc borate, 1.5 parts by weight of sodium molybdate and 2 parts by weight of an anti-aging agent.
In the step E, the mixing temperature is 110-130 ℃ and the mixing time is 20-50 min.
The invention makes the phosphogypsum and the fly ash become useful substances through reaction and recombination. The general reaction scheme of the principle is:
CaSO4(phosphogypsum)+Na2O·SiO2·Al2O3(fly ash) → Na2O·Al2O3+CaO·SiO2↓ + [ sulfur)]
From the reaction formula, CaO in phosphogypsum and SiO in fly ash are used2To produce calcium orthosilicate (CaO. SiO)2↓) to obtain sodium aluminate (Na) with excellent solubility2O·Al2O3). In the reaction formula [ sulfur ]]The method is characterized in that the main component of the metal sulfide generated by a raw material modifier adding process is FeS; and leaching the sodium aluminate in the clinker, and then floating the obtained precipitate to obtain FeS.
Advantageous effects
1. The invention comprehensively utilizes the industrial waste residue phosphogypsum and the fly ash, adds the modifier and the additive, then mixes, grinds, roasts, and carries out solid-liquid separation after being dissolved out by water grinding, thus obtaining products with distinct components, the products are respectively convenient to extract, and the utilization process of the phosphogypsum and the fly ash is very simple.
2. The invention mixes and grinds the phosphogypsum and the fly ash together with a modifier and an additive, roasts the mixture, and then carries out solid-liquid separation after the mixture is dissolved out by a water mill, thus obtaining a product with clear components, wherein valuable components can be extracted independently, thereby greatly improving the utilization rate of the phosphogypsum and the fly ash.
3. The invention grinds and roasts the industrial waste residue phosphogypsum and fly ash, the mixed additive and the modifier, and then carries out water mill dissolution and solid-liquid separation, the cost of the raw materials is low, the process is simple, and the main components of metal sulfide, meta-aluminate and silicate formed in the roasting process are distinct and can be extracted and recovered independently, thereby greatly improving the added values of the phosphogypsum and fly ash.
4. The method utilizes the phosphogypsum and the fly ash as raw materials, additives and modifiers are added, the calcined product is dissolved out by a water mill and is subjected to solid-liquid separation to obtain a product with clear components, the calcined product does not contain organic matters, the method is very beneficial to respectively extracting each component of the product in the later period, especially, liquid is obtained in the solid-liquid separation, and the sodium metaaluminate solution which is simply purified by calcium oxide is introduced into a CO solution2Gas (es)The washed aluminum hydroxide has high purity which can reach more than 99 percent, and is a good flame retardant additive raw material used as a rubber flame retardant.
5. The method for preparing the aluminum hydroxide by using the cheap industrial waste residue phosphogypsum and fly ash and adding a certain additive and modifier has the advantages of simple process, low raw material cost and low cost of the obtained aluminum hydroxide, can be used for producing the rubber flame retardant, can greatly reduce the production cost of the rubber flame retardant, and the rubber produced by adding the rubber flame retardant has good heat resistance and flame retardance.
To demonstrate the advantages of the present invention, the inventors made the following tests:
the rubber flame retardants prepared in examples 1 to 5 were used to prepare flame-retardant isoprene rubbers with isoprene rubber, the ratio of the amount of each rubber flame retardant to the amount of isoprene rubber was 1:3, and the prepared flame-retardant isoprene rubbers were subjected to self-extinguishing time and oxygen index detection to obtain the results shown in table 1.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention.
Examples of the invention
Example 1: a method for preparing acid and coproducing rubber flame retardant from phosphogypsum and fly ash comprises the following steps:
A. mixing phosphogypsum, fly ash, sodium sulfate and carbon, grinding to obtain raw material, mixing phosphogypsum and fly ash according to the weight ratio of 1:1.7, and adding sodium sulfate according to the Na contained in raw material2O and A12O3+Fe2O3Adding the raw materials in a total molecular ratio of 1:1, feeding the mixture of carbon accounting for 12% of the total weight of the raw materials into an industrial vertical kiln for roasting at 1050 ℃ for 5 hours to obtain clinker, carrying out water milling on the clinker for dissolution, and carrying out solid-liquid separation, wherein the volume ratio of liquid to solid is 3: 1;
B. b, carrying out flotation on the precipitate obtained by solid-liquid separation in the step A, separating out sulfide, roasting the separated sulfide for 5 hours at 1150 ℃ in a 40% oxygen-enriched environment, and absorbing smoke generated by roasting by adopting concentrated sulfuric acid after vanadium pentoxide catalytic reaction to prepare sulfuric acid;
C. adding analytically pure calcium oxide into the liquid obtained by the solid-liquid separation in the step A according to the proportion of 10g/L, heating to 95 ℃, stirring for 1h, and filtering to obtain a sodium metaaluminate solution;
D. c, introducing CO with the concentration of more than 37 percent into the sodium metaaluminate solution prepared in the step C2Gas until no precipitate is generated, washing the precipitate with distilled water, drying the washed precipitate in a drying oven at 95 ℃, and then grinding to obtain aluminum hydroxide;
E. and D, putting 30 parts by weight of the aluminum hydroxide prepared in the step D into a mixing roll, adding 30 parts by weight of fumed silica, 2 parts by weight of chlorinated paraffin, 3 parts by weight of hexabromocyclododecane, 3 parts by weight of zinc borate, 1 part by weight of sodium molybdate and 1 part by weight of antioxidant RD, and mixing for 20min at 110 ℃ to prepare the rubber flame retardant.
Example 2: a method for preparing acid and coproducing rubber flame retardant from phosphogypsum and fly ash comprises the following steps:
A. mixing phosphogypsum, fly ash, sodium sulfate and carbon, grinding to obtain raw material, mixing phosphogypsum and fly ash according to the weight ratio of 1.4:1, and adding sodium sulfate according to the Na contained in raw material2O and A12O3+Fe2O3Adding the raw materials in a total molecular ratio of 1:1, feeding the mixture of carbon accounting for 28% of the total weight of the raw materials into an industrial vertical kiln for roasting at 1350 ℃ for 1h to obtain clinker, carrying out water milling on the clinker for dissolution, and carrying out solid-liquid separation, wherein the liquid-solid volume ratio is 8:1 during separation;
B. b, carrying out flotation on the precipitate obtained by solid-liquid separation in the step A, separating out sulfide, roasting the separated sulfide at 1200 ℃ for 3h in a 45% oxygen-enriched environment, and absorbing smoke generated by roasting by adopting concentrated sulfuric acid after vanadium pentoxide catalytic reaction to prepare sulfuric acid;
C. adding analytically pure calcium oxide into the liquid obtained by solid-liquid separation in the step A according to the concentration of 7g/L, heating to 75 ℃, stirring for 2 hours, and filtering to obtain a sodium metaaluminate solution;
D. c, introducing CO with the concentration of more than 37 percent into the sodium metaaluminate solution prepared in the step C2Gas until no precipitate is generated, washing the precipitate with distilled water, drying the washed precipitate in a drying box at 105 ℃, and then grinding to prepare aluminum hydroxide;
E. and D, putting 40 parts by weight of the aluminum hydroxide prepared in the step D into a mixing roll, adding 40 parts by weight of fumed silica, 4 parts by weight of chlorinated paraffin, 5 parts by weight of hexabromocyclododecane, 5 parts by weight of zinc borate, 2 parts by weight of sodium molybdate and 3 parts by weight of antioxidant RD, and mixing for 50min at 130 ℃ to prepare the rubber flame retardant.
Example 3: a method for preparing acid and coproducing rubber flame retardant from phosphogypsum and fly ash comprises the following steps:
A. mixing phosphogypsum, fly ash, sodium sulfate and carbon, grinding to obtain raw material, mixing phosphogypsum and fly ash according to the weight ratio of 1.2:1.3, and adding sodium sulfate according to the Na contained in the raw material2O and A12O3+Fe2O3Adding the raw materials in a total molecular ratio of 1:1, feeding the raw materials into an industrial vertical kiln for roasting at 1200 ℃ for 3h according to the mixing ratio of carbon which is 20 percent of the total weight of the raw materials to obtain clinker, carrying out water milling dissolution on the clinker, and carrying out solid-liquid separation, wherein the liquid-solid volume ratio is 5:1 during the separation;
B. b, carrying out flotation on the precipitate obtained by solid-liquid separation in the step A, separating out sulfide, roasting the separated sulfide at 1200 ℃ for 4 hours in a 45% oxygen-enriched environment, and absorbing smoke generated by roasting by adopting concentrated sulfuric acid after vanadium pentoxide catalytic reaction to prepare sulfuric acid;
C. adding analytically pure calcium oxide into the liquid obtained by the solid-liquid separation in the step A according to 9g/L, heating to 85 ℃, stirring for 1.5h, and filtering to obtain a sodium metaaluminate solution;
D. c, introducing CO with the concentration of more than 37 percent into the sodium metaaluminate solution prepared in the step C2Gas until no precipitate is formed, washing the precipitate with distilled water, and drying the washed precipitate at 100 deg.CDrying in a box, and then grinding to prepare aluminum hydroxide;
E. and D, putting 35 parts by weight of the aluminum hydroxide prepared in the step D into a mixing roll, adding 35 parts by weight of fumed silica, 3 parts by weight of chlorinated paraffin, 4 parts by weight of hexabromocyclododecane, 4 parts by weight of zinc borate, 1.5 parts by weight of sodium molybdate and 2 parts by weight of antioxidant RD, and mixing for 35min at 120 ℃ to prepare the rubber flame retardant.
Example 4: a method for preparing acid and coproducing rubber flame retardant from phosphogypsum and fly ash comprises the following steps:
A. mixing phosphogypsum, fly ash, sodium sulfate and carbon, grinding to obtain raw material, mixing phosphogypsum and fly ash according to the weight ratio of 1.2:1.4, and adding sodium sulfate according to the Na contained in the raw material2O and A12O3+Fe2O3Adding the raw materials in a total molecular ratio of 1:1, feeding the raw materials with a carbon mixing ratio of 25% of the total weight of the raw materials into an industrial vertical kiln for roasting at a roasting temperature of 1220 ℃ for 3.5 hours to obtain clinker, carrying out water milling dissolution on the clinker, and carrying out solid-liquid separation with a liquid-solid volume ratio of 5: 1;
B. b, carrying out flotation on the precipitate obtained by solid-liquid separation in the step A, separating out sulfide, roasting the separated sulfide at 1200 ℃ for 4 hours in a 45% oxygen-enriched environment, and absorbing smoke generated by roasting by adopting concentrated sulfuric acid after vanadium pentoxide catalytic reaction to prepare sulfuric acid;
C. adding analytically pure calcium oxide into the liquid obtained by the solid-liquid separation in the step A according to 8g/L, heating to 85 ℃, stirring for 1.5h, and filtering to obtain a sodium metaaluminate solution;
D. c, introducing CO with the concentration of more than 37 percent into the sodium metaaluminate solution prepared in the step C2Gas until no precipitate is generated, washing the precipitate with distilled water, drying the washed precipitate in a drying oven at 100 ℃, and then grinding to obtain aluminum hydroxide;
E. and D, putting 32 parts by weight of the aluminum hydroxide prepared in the step D into a mixing roll, adding 32 parts by weight of fumed silica, 2.5 parts by weight of chlorinated paraffin, 3.5 parts by weight of hexabromocyclododecane, 3.5 parts by weight of zinc borate, 1.2 parts by weight of sodium molybdate and 1.1 parts by weight of antioxidant RD, and mixing for 30min at 115 ℃ to prepare the rubber flame retardant.
Example 5: a method for preparing acid and coproducing rubber flame retardant from phosphogypsum and fly ash comprises the following steps:
A. mixing phosphogypsum, fly ash, sodium sulfate and carbon, grinding to obtain raw material, mixing phosphogypsum and fly ash according to the weight ratio of 1.2:1.1, and adding sodium sulfate according to the Na contained in the raw material2O and A12O3+Fe2O3Adding the raw materials in a total molecular ratio of 1:1, feeding the mixture of carbon accounting for 17% of the total weight of the raw materials into an industrial vertical kiln for roasting at 1100 ℃ for 4 hours to obtain clinker, carrying out water milling on the clinker for dissolution, and carrying out solid-liquid separation, wherein the volume ratio of liquid to solid is 5: 1;
B. b, carrying out flotation on the precipitate obtained by solid-liquid separation in the step A, separating out sulfide, roasting the separated sulfide at 1200 ℃ for 4 hours in a 45% oxygen-enriched environment, and absorbing smoke generated by roasting by adopting concentrated sulfuric acid after vanadium pentoxide catalytic reaction to prepare sulfuric acid;
C. adding analytically pure calcium oxide into the liquid obtained by the solid-liquid separation in the step A according to 8g/L, heating to 85 ℃, stirring for 1.5h, and filtering to obtain a sodium metaaluminate solution;
D. c, introducing CO with the concentration of more than 37 percent into the sodium metaaluminate solution prepared in the step C2Gas until no precipitate is generated, washing the precipitate with distilled water, drying the washed precipitate in a drying oven at 100 ℃, and then grinding to obtain aluminum hydroxide;
E. and D, putting 38 parts by weight of the aluminum hydroxide prepared in the step D into a mixing roll, adding 38 parts by weight of fumed silica, 3.5 parts by weight of chlorinated paraffin, 4.3 parts by weight of hexabromocyclododecane, 4.5 parts by weight of zinc borate, 1.6 parts by weight of sodium molybdate and 2.5 parts by weight of an anti-aging agent RD, and mixing for 40min at 125 ℃ to prepare the rubber flame retardant.
Claims (8)
1. A method for preparing acid and coproducing rubber flame retardant from phosphogypsum and fly ash is characterized by comprising the following steps:
A. mixing and grinding phosphogypsum, fly ash, additive and modifierGrinding the raw materials into raw materials, feeding the raw materials into a kiln for roasting to obtain clinker, carrying out water grinding dissolution on the clinker, and carrying out solid-liquid separation; the additive is sodium carbonate, sodium sulfate or caustic soda; the modifier is anthracite, carbon or coal gangue; the kiln is an industrial rotary kiln, an industrial tunnel kiln or an industrial vertical kiln; in the raw material, phosphogypsum and fly ash are mixed according to the weight ratio of 1-1.4:1-1.7, and the additive is added according to the Na contained in the raw material2O and Al2O3+Fe2O3The total molecular ratio is 1:1, and the mixing ratio of the modifier is 12-28% of the total weight of the raw material; the roasting temperature is 1050-; the liquid-solid volume ratio during water milling dissolution is 3-8: 1;
B. b, carrying out flotation on the precipitate obtained by solid-liquid separation in the step A, separating out sulfide, roasting the separated sulfide, carrying out catalytic reaction on the flue gas generated by roasting through vanadium pentoxide, and absorbing the flue gas by adopting concentrated sulfuric acid to prepare sulfuric acid;
C. adding calcium oxide into the liquid obtained by solid-liquid separation in the step A, heating, stirring and filtering to prepare a sodium metaaluminate solution;
D. c, introducing CO into the sodium metaaluminate solution prepared in the step C2Until no precipitate is generated, washing the precipitate with distilled water, drying the washed precipitate, and grinding to obtain aluminum hydroxide;
E. and D, putting the aluminum hydroxide prepared in the step D into a mixing roll, adding fumed silica, chlorinated paraffin, hexabromocyclododecane, zinc borate, sodium molybdate and an anti-aging agent, and mixing to obtain the rubber flame retardant.
2. The method for co-producing rubber flame retardant by using phosphogypsum and fly ash to prepare acid according to claim 1, which is characterized in that: in the step B, the roasting temperature is 1150-1250 ℃; the time is 3-5 h; the condition is that the sulfide is put in 40-50% oxygen-rich environment.
3. The method for co-producing rubber flame retardant by using phosphogypsum and fly ash to prepare acid according to claim 1, which is characterized in that: in the step C, the calcium oxide is analytically pure, and the using amount is 7-10 g/L; the heating temperature is 75-95 ℃; the stirring time is 1-2 h.
4. The method for co-producing rubber flame retardant by using phosphogypsum and fly ash to prepare acid according to claim 1, which is characterized in that: in step D, the CO2CO in gas2Is greater than 37%; the drying temperature is 95-105 ℃.
5. The method for co-producing rubber flame retardant by using phosphogypsum and fly ash to prepare acid according to claim 1, which is characterized in that: in the step E, the anti-aging agent is an anti-aging agent RD.
6. The method for co-producing rubber flame retardant by using phosphogypsum and fly ash to prepare acid according to claim 1, which is characterized in that: in the step E, the rubber flame retardant comprises, by weight, 30-40 parts of aluminum hydroxide, 30-40 parts of fumed silica, 2-4 parts of chlorinated paraffin, 3-5 parts of hexabromocyclododecane, 3-5 parts of zinc borate, 1-2 parts of sodium molybdate and 1-3 parts of an anti-aging agent.
7. The method for co-producing rubber flame retardant by using phosphogypsum and fly ash to prepare acid according to claim 1, which is characterized in that: the rubber flame retardant comprises, by weight, 35 parts of aluminum hydroxide, 35 parts of fumed silica, 3 parts of chlorinated paraffin, 4 parts of hexabromocyclododecane, 4 parts of zinc borate, 1.5 parts of sodium molybdate and 2 parts of an anti-aging agent.
8. The method for co-producing rubber flame retardant by using phosphogypsum and fly ash to prepare acid according to claim 1, which is characterized in that: in the step E, the mixing temperature is 110-130 ℃, and the mixing time is 20-50 min.
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