CN109913953B - Method for treating solid residues containing calcium sulfate in preparation process of pentamethylene diamine - Google Patents
Method for treating solid residues containing calcium sulfate in preparation process of pentamethylene diamine Download PDFInfo
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Abstract
The invention discloses a method for treating calcium sulfate-containing solid residues in a pentanediamine preparation process, which comprises the steps of adding water into the calcium sulfate-containing solid residues generated in the pentanediamine preparation process to prepare slurry, then adding a sulfuric acid solution to adjust the pH value to 5.0-6.5, acidifying at the temperature of 60-120 ℃ to obtain a calcium sulfate-containing suspension, then adding a crystal form conversion agent, carrying out hydrothermal treatment at the temperature of 100-160 ℃ for 1-6 h to obtain a calcium sulfate-containing whisker suspension, finally carrying out solid-liquid separation, and washing, drying and calcining filter residues to obtain calcium sulfate whiskers. The method effectively solves the problem of solid slag treatment containing calcium sulfate generated in the production process of the pentamethylenediamine, reduces the pressure of subsequent treatment of solid waste, reduces the environmental burden, and successfully prepares the calcium sulfate whiskers by recycling the solid waste, thereby forming a new added value of products. The calcium sulfate whisker prepared by the method is used in PVC plastic products, and test results show that the performance of the plastic products is remarkably improved.
Description
Technical Field
The invention belongs to the field of industrial waste residue treatment, and particularly relates to a method for treating calcium sulfate-containing solid residues generated in a process of preparing pentamethylene diamine by a biological method.
Background
In recent years, many biological processes for producing pentamethylenediamine have been reported, and a microbial fermentation process is often used. Basically, the method can be divided into three steps, (1) lysine is produced by fermentation: producing lysine by using biomass as a raw material; (2) fermentation and enzymatic conversion of decarboxylase: using lysine as a raw material, and decarboxylating the lysine through decarboxylase to produce 1, 5-pentanediamine; (3) separating, extracting and purifying the product pentanediamine. Since the decarboxylase action is neutral and the pentanediamine exists in the form of ions under neutral conditions, the alkali adjustment is an essential step if the pure molecular pentanediamine is obtained. According to previous reports, calcium hydroxide and calcium oxide are mostly used for adjusting alkali. As the pentanediamine contains two amino groups, 2 molecules of hydroxyl are consumed by 1 molecule of pentanediamine, so that the consumption of alkali is large, and after the alkali is added, the alkali can react with sulfate radicals and carbonate radicals existing in a solution to generate a large amount of precipitation mixture containing calcium, so that the treatment is difficult, solid residues are formed, and great pressure is caused on the environment.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art, and provides a high-valued treatment method of calcium sulfate-containing solid slag.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the treatment method of the solid slag containing calcium sulfate in the preparation process of the pentamethylene diamine comprises the following steps:
(1) adding water into the calcium sulfate-containing solid residues generated in the preparation process of the pentamethylene diamine to prepare slurry, then adding a sulfuric acid solution to adjust the pH value to 5.0-6.5, and acidifying at the temperature of 60-120 ℃ to obtain a calcium sulfate-containing suspension;
(2) adding a crystal form converting agent into the calcium sulfate-containing suspension obtained in the step (1), and performing hydrothermal treatment at 100-160 ℃ for 1-6 h to obtain a calcium sulfate-containing whisker suspension;
(3) and (3) carrying out solid-liquid separation on the calcium sulfate whisker-containing suspension obtained in the step (2), and washing, drying and calcining filter residues to obtain the calcium sulfate whiskers.
Specifically, in the step (1), the solid residue containing calcium sulfate comprises calcium sulfate, calcium carbonate, calcium hydroxide, pigment and foreign protein; wherein, the three components of calcium sulfate, calcium carbonate and calcium hydroxide account for more than 85 percent of the total mass of the solid slag.
The mixing mass ratio of the calcium sulfate-containing solid slag to water is 1: 1-2.
The mass fraction of the sulfuric acid solution is 30-60 wt%, and the aim of acidification is to completely convert solid residues into calcium sulfate.
In the step (2), the crystal form converting agent is any one or a composition of more than two of aluminate, titanate, silane, isopropyl ester and KCL, and the dosage of the crystal form converting agent is 0.2-1% of the total mass of calcium sulfate in the calcium sulfate-containing suspension.
Preferably, in the step (3), the drying temperature is 60-150 ℃ and the drying time is 0.5-8 h.
The calcining temperature is 500-800 ℃, and the time is 2-6 h.
Calcium sulfate whiskers, also called gypsum whiskers, are important inorganic salt crystals, which can be divided into three types, namely anhydrous, semi-hydrated and dihydrate, according to the amount of moisture content in the crystals, wherein the anhydrous calcium sulfate whiskers have the highest strength. Compared with other crystals, the calcium sulfate whisker has the advantages of high temperature resistance, acid and alkali resistance, good toughness, high strength, chemical corrosion resistance and the like, and has lower price in inorganic whisker materials and higher cost performance. The application range of the gypsum whisker is very wide, and the gypsum whisker is mainly applied to the paper industry, the building material industry, the ceramic industry, the mechanical industry and the light industry. At present, the method for preparing the gypsum whisker has a plurality of methods with different characteristics, and the most common method is a hydrothermal method. The solid calcium sulfate slag formed in the preparation process of the pentanediamine is complex in components, mainly comprises calcium sulfate, calcium carbonate, calcium hydroxide, pigments, foreign proteins and the like, for example, existing carbonate ions generate a competitive relationship with sulfate radicals in the formation process of the calcium sulfate whisker, and the growth rate of the end face of the whisker is inhibited, so that the formation of the whisker is inhibited. This brings great difficulty to the preparation of calcium sulfate whisker by hydrothermal method.
According to the invention, solid residues are firstly converted into calcium sulfate turbid liquid through acidification, then a crystal form converting agent is added, calcium sulfate whisker containing suspension is obtained through hydrothermal treatment, and finally filter residues are separated and calcined to obtain calcium sulfate whiskers, so that high-valued treatment of wastes is realized, and the environmental protection of the process is improved.
Has the advantages that:
1. the method effectively solves the problem of solid slag treatment containing calcium sulfate generated in the production process of the pentamethylenediamine, reduces the pressure of subsequent treatment of solid waste, reduces the environmental burden, and successfully prepares the calcium sulfate whiskers by recycling the solid waste, thereby forming a new added value of products.
2. According to the invention, titanate and the like can be used as good crystal form converting agents for preparing the calcium sulfate crystal whiskers, so that good crystal conversion can be still realized when calcium sulfate precipitates in waste residues containing complex components.
3. The calcium sulfate whisker prepared by the method is used in PVC plastic products, and test results show that the performance of the plastic products is remarkably improved.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
Fig. 1 is an optical microscope image (16 × 10 times) of the calcium sulfate whisker product prepared in example 1.
Fig. 2 is an infrared spectrum of the calcium sulfate whisker product prepared in example 1.
FIG. 3 is an X-ray powder diffraction pattern of the calcium sulfate whisker product prepared in example 1.
FIG. 4 is a thermal analysis TG-DSC spectrum of the calcium sulfate whisker product prepared in example 1.
Detailed Description
The invention will be better understood from the following examples.
In the following examples, whiteness measurements were carried out using a ZBD type whiteness meter; refer to the method of GB 2913-82.
Example 1
2L of the alkali-adjusted pentamethylenediamine conversion solution (pH 12.5) was taken, and suction filtration was performed using a Bush funnel to separate the solid from the liquid. Adding water with one time of mass into solid residues containing calcium sulfate, mainly comprising calcium sulfate, calcium carbonate, calcium hydroxide, pigment, and foreign protein, concocting into slurry, subjecting the obtained slurry to ultrasound treatment for 20min, and gradually pumping 30 wt% of H into the slurry by using a peristaltic pump2SO4And in the process, stirring is kept, and the reaction is carried out at room temperature, wherein the pH is adjusted to 5.5, and the temperature is 60 ℃, so that all solid residues are converted into calcium sulfate precipitates. And after stirring for 1h, adding aluminate into the calcium sulfate-containing suspension to serve as a crystal transformation agent so as to induce the generation of calcium sulfate whiskers. After fully stirringDirectly transferring the slurry into a stainless steel high-pressure reaction kettle, setting the temperature in the high-pressure reaction kettle at 130 ℃, keeping the process stirring, reacting for 5 hours, discharging the slurry into a tank, performing solid-liquid separation by suction filtration, washing solid filter residue with hot water, then drying the solid filter residue in an oven at 80 ℃, transferring the solid filter residue into a high-temperature furnace at 750 ℃ to calcine for 3 hours after 3 hours, then cooling to room temperature to obtain the calcium sulfate whisker, and measuring the bulk density of the calcium sulfate whisker to be 0.22g/ml, the whiteness to be 89, the length-diameter ratio to be 1: 50-80, wherein the thermal analysis result shows that the water content is 0.
The optical microscope picture of the prepared calcium sulfate whisker product is shown in figure 1, the infrared spectrogram is shown in figure 2,
the X-ray powder diffraction spectrum is shown in figure 3, and the thermal analysis TG-DSC spectrum is shown in figure 4. The length-diameter ratio of the prepared calcium sulfate whisker product is about 1: 20-80, and the whisker is slender and uniform. The crystallinity of the obtained crystal whisker is very high as can be seen from an X-ray powder diffraction spectrogram, and the obtained crystal whisker does not contain crystal water and has stable product as can be seen from a thermal analysis spectrogram.
Example 2
2L of the alkali-adjusted pentamethylenediamine conversion solution (pH 12.3) was taken, and suction filtration was performed using a Bush funnel to separate the solid from the liquid. Adding water with one time of mass into solid residues containing calcium sulfate, mainly comprising calcium sulfate, calcium carbonate, calcium hydroxide, pigment, and foreign protein, concocting into slurry, subjecting the obtained slurry to ultrasound treatment for 20min, and gradually pumping 45 wt% of H into the slurry by using a peristaltic pump2SO4And in the process, stirring is kept, and the reaction is carried out at room temperature, wherein the pH is adjusted to 5.0, and the temperature is 90 ℃, so that all solid residues are converted into calcium sulfate precipitates. And after stirring for 2 hours, adding silane serving as a crystal form conversion agent into the calcium sulfate-containing suspension to induce the generation of calcium sulfate whiskers. After fully stirring, directly transferring the slurry into a stainless steel high-pressure reaction kettle, setting the temperature in the high-pressure reaction kettle to be 140 ℃, keeping stirring in the process, reacting for 4 hours, discharging the slurry into a tank, performing solid-liquid separation through suction filtration, washing solid filter residue with hot water, then drying the solid filter residue in a 60 ℃ drying oven, after 8 hours, transferring the solid filter residue into a 500 ℃ high-temperature furnace for calcining for 6 hours, and then cooling to room temperatureThe obtained calcium sulfate whisker has the bulk density of 0.24g/ml, the whiteness of 91 and the length-diameter ratio of 1: 50-85, and the thermal analysis result shows that the water content of the calcium sulfate whisker is 0.
Example 3
2L of the alkali-adjusted pentamethylenediamine conversion solution (pH 12.0) was taken, and subjected to suction filtration using a Bush funnel to separate a solid from a liquid. Adding water with one time of mass into solid residues containing calcium sulfate, mainly comprising calcium sulfate, calcium carbonate, calcium hydroxide, pigment, and foreign protein, concocting into slurry, subjecting the obtained slurry to ultrasound treatment for 20min, and gradually pumping 60 wt% of H into the slurry by using a peristaltic pump2SO4And in the process, stirring is kept, and the reaction is carried out at room temperature, wherein the pH is adjusted to 5.8, and the temperature is 120 ℃, so that all solid residues are converted into calcium sulfate precipitates. And after stirring for 2 hours, adding aluminate into the calcium sulfate-containing suspension to serve as a crystal transformation agent so as to induce the generation of calcium sulfate whiskers. And after fully stirring, directly transferring the slurry into a stainless steel high-pressure reaction kettle, setting the temperature in the high-pressure reaction kettle at 160 ℃, keeping stirring during the process, reacting for 3 hours, discharging the slurry into a tank, performing solid-liquid separation through suction filtration, washing solid filter residue with hot water, then drying the solid filter residue in a 90 ℃ oven, transferring the solid filter residue into a 800 ℃ high-temperature furnace for calcining for 2 hours after 2 hours, then cooling to room temperature to obtain the calcium sulfate whisker, and measuring the bulk density of the calcium sulfate whisker to be 0.21g/ml, the whiteness to be 87 and the length-diameter ratio to be 1: 40-80, wherein the thermal analysis result shows that the water content of the calcium sulfate whisker is 0.
Example 4
And (3) preparing the PVC plastic plate by adopting the calcium sulfate whiskers prepared in the embodiments 1-3.
The formula of the blank PVC plastic plate is as follows: 100g of polyvinyl chloride, 5g of calcium stearate, 3g of tributyl citrate, 3g of phthalate, 2g of polyacrylamide, 3g of sodium tripolyphosphate, 2g of stearic acid, 4g of isooctyl dimethyldimercaptoacetate tin and 13g of a modification auxiliary agent; wherein the modification auxiliary agent comprises 5g of magnesium chloride, 3g of sodium carboxymethylcellulose, 2g of ethylene diammonium tetraacetic acid and 3g of epoxy tetrahydrodioctyl phthalate.
And uniformly mixing the samples, placing the mixture into an internal mixer for mixing for 3 minutes at the mixing temperature of 140 ℃, injecting the mixture into a double-screw extruder by a feeding screw, extruding the mixture by the double-screw extruder, molding and shaping the mixture by a mold, and cutting the mixture to obtain the PVC plastic plate.
In the same production method, 10g of the calcium sulfate whiskers prepared in examples 1 to 3 were filled in PVC (mass ratio of the calcium sulfate whiskers to the PVC was 1: 10), and PVC plastic sheets reinforced with the calcium sulfate whiskers were prepared and subjected to a plastic bending performance test.
The bending properties of the blank PVC plastic sheet are shown in Table 1; example 1 the bending properties of the PVC plastic sheet reinforced with calcium sulfate whiskers are shown in table 2; example 2 the bending properties of the PVC plastic sheet reinforced with calcium sulfate whiskers are shown in table 3; example 3 the bending properties of the PVC plastic sheet reinforced with calcium sulfate whiskers are shown in table 4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
The results show that compared with the plastic directly made of PVC, the plastic plate made of PVC with calcium sulfate whiskers added in PVC has the flexural modulus of the PVC plastic plate reinforced by calcium sulfate whiskers in example 1 improved by 11.5%, the flexural modulus of the PVC plastic plate reinforced by calcium sulfate whiskers in example 2 improved by 13.4%, and the flexural modulus of the PVC plastic plate reinforced by calcium sulfate whiskers in example 3 improved by 10.3%.
The invention provides a thought and a method for treating calcium sulfate-containing solid slag in a pentanediamine preparation process, and particularly provides a method and a way for realizing the technical scheme, the method and the way are only preferred embodiments of the invention, and it should be noted that for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and the decorations are also regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (1)
1. The method for treating the solid slag containing calcium sulfate in the preparation process of the pentamethylene diamine is characterized by comprising the following steps of:
(1) adding water into the calcium sulfate-containing solid residues generated in the preparation process of the pentamethylene diamine to prepare slurry, then adding a sulfuric acid solution to adjust the pH value to 5.0-6.5, and acidifying at the temperature of 60-120 ℃ to obtain a calcium sulfate-containing suspension;
(2) adding a crystal form converting agent into the calcium sulfate-containing suspension obtained in the step (1), and performing hydrothermal treatment at 100-160 ℃ for 1-6 h to obtain a calcium sulfate-containing whisker suspension;
(3) carrying out solid-liquid separation on the calcium sulfate whisker containing suspension obtained in the step (2), and washing, drying and calcining filter residues to obtain calcium sulfate whiskers;
(4) preparing a PVC plastic plate from the obtained calcium sulfate whisker;
in the step (1), the solid residue containing calcium sulfate comprises calcium sulfate, calcium carbonate, calcium hydroxide, pigment and foreign protein; wherein, the three components of calcium sulfate, calcium carbonate and calcium hydroxide account for more than 85 percent of the total mass of the solid slag;
in the step (1), the mixing mass ratio of the calcium sulfate-containing solid slag to water is 1: 1-2;
in the step (1), the mass fraction of the sulfuric acid solution is 30-60 wt%;
in the step (2), the crystal form converting agent is one or a composition of more than two of aluminate and silane, and the dosage of the crystal form converting agent is 0.2-1% of the total mass of calcium sulfate in the calcium sulfate-containing suspension;
in the step (3), the drying temperature is 60-150 ℃ and the drying time is 0.5-8 h;
in the step (3), the calcining temperature is 500-800 ℃, and the time is 2-6 h.
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| CN102352535B (en) * | 2011-09-22 | 2014-01-29 | 东莞上海大学纳米技术研究院 | Method for preparing calcium sulfate crystal whiskers from desulfurized gypsum under normal pressure |
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