CN102321396A - Process for depolymerizing and purifying high-performance and environment-friendly phenylalanine ammonia lyase (PAL) flame-retardant material - Google Patents
Process for depolymerizing and purifying high-performance and environment-friendly phenylalanine ammonia lyase (PAL) flame-retardant material Download PDFInfo
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Abstract
The invention relates to the technical field of flame-retardant materials, in particular to a process for depolymerizing and purifying a high-performance and environment-friendly phenylalanine ammonia lyase (PAL) flame-retardant material, and solves the technical problems that the prior art is unreasonable and the like. The process comprises the following steps of: A, depolymerizing; and B, purifying. Compared with the prior art, the process for depolymerizing and purifying the high-performance and environment-friendly PAL flame-retardant material has the advantages that: the dynamic action of hydration expansive force generated by hydration of a high-speed water medium and a substance and repulsive force of a diffused electric double layer formed by fully hydrating interlayer cations is fully exerted, disintegration and dispersion are promoted, the material is separated from impurities and purified (the medium water can be recycled), chemical impurities are prevented from being introduced and environment pollution harm is avoided in the conventional medicament floatation, high-purity micro/nano PAL material powder is prepared, and a material basis is provided for preparing the high-performance and environment-friendly flame-retardant material.
Description
Technical field
The present invention relates to the fire retardant material technical field, especially relate to a kind of high-performance environment protection type PAL fire retardant material depolymerization purifying technique.
Background technology
Fire-retardant essential for human beings'health and safety, The development in society and economy, its significance is self-evident.In self the fire-fighting demand in fields such as building, chemical industry, military affairs and traffic and the field of tool inflammableness macromolecular material, fire retardant material is reducing ratio aspect the fire hazard up to more than 70%.Facts have proved that fire retardant material is avoided heavy economic losses and the aspect of preserving the ecological environment reducing the fire loss of life and personal injury; All bring into play big emphatically effect; Thereby, the research of fire retardant and fire retardant material, production and application, significant for socio-economic development " mankind and environment ".At present, common fire retardant mainly contains halogenated flame retardant, silicon-series five-retardant, phosphorus flame retardant, triazine flame retardant and inorganic combustion inhibitor.China is main with halogen containing flame-retardants such as bromine system, chlorine systems; Though the Halogen fire retardant material has good flame-retardant effect; But can discharge a large amount of smog and poisonous, harmful corrosive gases during general Halogen fire retardant material presence of fire, personnel and precision instrument are brought very big infringement.Strictness along with the global environment rules; China requires the reinforcement of dynamics to flame-retarded technology; People require increasingly high to fire safety and goods fire-retardant, Halogen, low cigarette, low toxicity, high-performance environment protection type flame-proof agent have become the target of socio-economic development and the harmonious pursuit of environment.
The PAL material is the green flame retardant of excellent performance, disturbs intercalation, peel ply, the chain flame retarding construction function of supporting component of combustion but have, and contains multiple ignition-proof element (Si, P, S, B) and press down cigarette element (Mo, Fe, Mg, Zn, Cn).The structure construction of PAL material is the structure of layer, chain, fibrous crystalline structure and nano level hole passage.It is an oblique system, and crystalline structure belongs to 2:1 type non-metallic minerals, promptly two-layer silicon-oxy tetrahedron folder one deck magnesium (aluminium) octahedron, and its tetrahedron and octahedral arrangement mode are laminate structure.In each 2:1 layer, the tetrahedron corner is pushed up at a certain distance direction and is put upside down form layers, chain combination characteristic.Form parallel at tetrahedron bar interband with chain; The passage that runs through skeleton; Channel cross-section is about 0.37nm * 0.63nm; Passage is that water molecules is filled, for the zeolite water (H2O) that is parallel to fiber and with mg ion coordinate crystal water (OH2), have surface adsorption water (H2O) and with octahedral cations coordinate water of constitution (OH).Its crystalline structure is a needle-like, is made up of elongated hollow tube.The unevenness on PAL material surface micromorphology performance structure surface rises and falls, and especially cleavage surface is very coarse, has the step of 1-2nm to occur, and presents the complicated micromorphology of distortion and spiral.Parallel fibers tunnel hole accounts for more than 1/2 of fiber volume, and interior external surface area is considerable, and the duct effect is remarkable.Combine with molecular linkage between the PAL material layer, even K+, Na+ are arranged, K-O, also much smaller than the linkage force of Si-O or Mg-O, water molecules, atoms metal, organic molecule can get into interlayer to the bonding force of Na-O key, make interfloor distance (interlamination region) that mutability arranged.The PAL material has unique layer, chain crystalline structure, has given PAL material particular performances.
Natural nano-mineral adsorbs each other usually or inlays, and is polymer state output, also is mixed with different quantities impurity, thereby the mineral material nano effect can't be brought into play.And inorganic fire-retarded the material that uses mostly at present is generally micron order, and fire-retardant loading level is big, and flame retarding efficiency is not high, and the problem of caused technology and product performance all compares seriously.Its mechanism reason is that micro materials can't realize that nanoparticle forms the structure and the form of nano composite material in polymeric matrix, and directly affect matrix material fire-retardant, strengthen overall performance such as mechanical characteristic.The more important thing is and affect and the consistency of polymeric matrix and the dispersiveness in polymeric matrix.Uses at present usually employing chemical flotation agent (medicament) or disperse as media implementation with non-aqueous solution.Above any way has all been introduced chemical, brings new impurity into for product (raw material), and environment is caused new pollution, need take disposal technology technology and increase input.
Summary of the invention
The objective of the invention is provides a kind of polymerization that can break between high-purity PAL material to the problems referred to above, makes it to form dispersive nanometer or submicron monomer, and can not cause the high-performance environment protection type PAL fire retardant material depolymerization purifying technique of environmental pollution.
For achieving the above object, the present invention has adopted following technical proposal: this high-performance environment protection type PAL fire retardant material depolymerization purifying technique is characterized in that this technology comprises the steps:
A, depolymerization: adopt target plate formula flow kibbler to carry out depolymerization and disperse; Be that medium carries high-purity PAL material promptly, bump against that material and target plate are in high velocity impact, bump with the fixedly target plate that is provided with the high speed flow; The high-speed functions of flow finally changes the crushing energy of material into, makes material broken;
B, purification: adopt the screw propulsion whizzer to realize purifying; Promptly in screw centrifuge screw rod propelled at high velocity process; Utilize the action of gravity of material particles size; Spiral separates the material of different-grain diameter, and control depolymerization dispersive paste consistency, front end can obtain from the subparticle of the different-grain diameter of＜100nm-10 μ m.
Mix in the PAL material feedstock impurity such as chlorite, illite, feldspar and carbonate are arranged; Fully compatiblely in matrix also need the PAL material of certain purity and micro/nano level with homodisperse, thus need disperse through depolymerization, warp separates with impurity and the technical matters of purifying prepares high-purity PAL material.In addition, though the PAL material is natural nonmetal nano-mineral, the nanoparticle material property is arranged; But owing to there is interfloor distance (interlamination region), characteristics of particles and interlamination region structure are prone to be polymer; Thereby need be through depolymerization; And it is fully dissociated and high dispersing in medium, could realize that the consistency in the polymeric matrix is good, dispersed height, thereby strengthen overall performances such as it is fire-retardant, mechanical characteristic.Therefore, the stabilization stabilization of purifying and Depolymerization Technique and technology, the optimization of flow process is to guarantee the layered nano PAL flame-retardant material flame retardant properties and realize the basis of industrialization, most important technical matters.
What the micro-nano powder technology of preparing was advanced is high speed flow ability method, and it is divided into air-flow and two kinds of forms of flow.With regard to high speed flow ability method, flow is pulverized has the fineness higher than comminution by gas stream, for very difficult some the micro-nano material realized in the comminution by gas stream field of force, serves as when pulverizing the field of force, then might realize micro-nanoization with flow power.In addition, serve as to pulverize in the process in the field of force with flow power, can avoid static, spark and partial temperature too high, thereby crushing process is comparatively safe.Fluid medium has good immersional wetting to material, can significantly reduce the particulate surface energy, reduces the required stress that ruptures; And from the process of particle fracture, according to the crack propagation condition, the fluid medium molecular adsorption can reduce the required external stress of crack propagation at fresh surface, promotes the expansion of crackle, and prevents the closed again of newborn crackle.If water medium; The aquation of material and water (water-swelling) effect reduces material grains volumetric expansion, hardness, reduces depolymerization and disperses required surging force; The positively charged ion aquation break away to form diffusion double layer and strengthens depolymerization and disperse between the particle nanometer layer, realization and separate impurities and obtain purification.The adding of medicament, the generation foam breaks and has encircled hydration and positively charged ion diffusion double layer, therefore, except that introducing impurity and damaging the environment, has checked depolymerization, the reduction dispersion effect of material grains on the contrary, and the purpose that separation is purified is difficult to realize.The present invention makes full use of the PAL material in water medium camber dispersive natural endowment property characteristics, and employing water is that fluid medium, no medicament add, and integrates flow process reasonableness, non-secondary pollution and resources circulation economy characteristic in one, prepares high-purity PAL material.
The raw material of PAL material is the sedimentary natural nonmetal silicates mineral of marine facies (semiclosed salty lake), is polar material, meets water the hydration swelling effect can take place, and gets into formation diffusion double layer in back in the water, further expands, and makes the mineral volume increase 8-20 doubly.Hydration weakens and has destroyed intergranular connection; Make particle along existing combination vulnerable area (like the set face of uncracked bedding, schistosity, wall reason, mineral grain and the mineral face etc. that dissociates); Form new crack; Make grain breakage, reduce the particulate mechanical strength, pulverize for further flow and reduced energy consumption.
Technical matters based on high-purity fully, the fine PAL material of the high speed flow legal system powder of the no medicament of ydrodynamics principle; Because the hydration swelling that the hydration of high speed flow and material produces and two electric depolymerization power of repelling; Height of materials is disperseed, accomplish miniaturization.Utilize differently, realize separating and purifying with impurity through the spiral centrifugal device with the gravity of impurity.Technological process of the present invention does not have waste gas, discharge of wastewater, and waste residue can be processed as agricultural siliceous fertilizer and macromolecular material strengthening agent WHITE CARBON BLACK, has realized that " environmentally friendly ", resource utilization are close to 100% " resources conservation ".
The present invention uses no medicament high speed flow law technology and depolymerization dispersion and the purification separating technology based on the ydrodynamics principle; The hydration swelling power of having given full play to the hydration of high speed water medium and material and having produced; The dynamic action of the diffusion double layer repulsive force that forms with the abundant aquation of interlayer cation; Promote to disintegrate disperse, separate with impurity and realize purifying (WATER AS FLOW MEDIUM reusable edible), avoided traditional medicament flotation to introduce the harm of impurity atom and contaminate environment; Formulate out high-purity, micro-nano PAL material powder, for manufacturing high-performance, environmental protection flame retardant material provide material foundation.
In above-mentioned high-performance environment protection type PAL fire retardant material depolymerization purifying technique, in above-mentioned steps A, the paste consistency after depolymerization disperses is 15%-20%.
In above-mentioned high-performance environment protection type PAL fire retardant material depolymerization purifying technique, in above-mentioned step B, the rotating speed of screw centrifuge is controlled at 1500r/min-2500r/min.
In above-mentioned high-performance environment protection type PAL fire retardant material depolymerization purifying technique, the PAL material content in described high-purity PAL material is 90%-98%.
Compared with prior art; The advantage of this high-performance environment protection type PAL fire retardant material depolymerization purifying technique is: given full play to the hydration of high speed water medium and material and the dynamic action of the diffusion double layer repulsive force that the abundant aquation of the hydration swelling power that produces and interlayer cation forms; Promote to disintegrate and disperse; Separate and realize purifying (WATER AS FLOW MEDIUM reusable edible) with impurity; Avoided traditional medicament flotation to introduce the harm of impurity atom and contaminate environment, formulated out high-purity, micro-nano PAL material powder, for manufacturing high-performance, environmental protection flame retardant material provide material foundation.
Embodiment
This high-performance environment protection type PAL fire retardant material depolymerization purifying technique comprises the steps:
A, depolymerization: adopt target plate formula flow kibbler to carry out depolymerization and disperse; Be that medium carries high-purity PAL material promptly, bump against that material and target plate are in high velocity impact, bump with the fixedly target plate that is provided with the high speed flow; The high-speed functions of flow finally changes the crushing energy of material into, makes material broken.Paste consistency after depolymerization disperses is 15%-20%.PAL material content in described high-purity PAL material is 90%-98%.
B, purification: adopt the screw propulsion whizzer to realize purifying; Promptly in screw centrifuge screw rod propelled at high velocity process; Utilize the action of gravity of material particles size; Spiral separates the material of different-grain diameter, and control depolymerization dispersive paste consistency obtains the subparticle less than the different-grain diameter of 100nm-10 μ m.The rotating speed of screw centrifuge is controlled at 1500r/min-2500r/min.
Mix in the PAL material feedstock impurity such as chlorite, illite, feldspar and carbonate are arranged; Fully compatiblely in matrix also need the PAL material of certain purity and micro/nano level with homodisperse, thus need disperse through depolymerization, warp separates with impurity and the technical matters of purifying prepares high-purity PAL material.In addition, though the PAL material is natural nonmetal nano-mineral, the nanoparticle material property is arranged; But owing to there is interfloor distance (interlamination region), characteristics of particles and interlamination region structure are prone to be polymer; Thereby need be through depolymerization; And it is fully dissociated and high dispersing in medium, could realize that the consistency in the polymeric matrix is good, dispersed height, thereby strengthen overall performances such as it is fire-retardant, mechanical characteristic.Therefore, the stabilization stabilization of purifying and Depolymerization Technique and technology, the optimization of flow process is to guarantee the layered nano PAL flame-retardant material flame retardant properties and realize the basis of industrialization, most important technical matters.
What the micro-nano powder technology of preparing was advanced is high speed flow ability method, and it is divided into air-flow and two kinds of forms of flow.With regard to high speed flow ability method, flow is pulverized has the fineness higher than comminution by gas stream, for very difficult some the micro-nano material realized in the comminution by gas stream field of force, serves as when pulverizing the field of force, then might realize micro-nanoization with flow power.In addition, serve as to pulverize in the process in the field of force with flow power, can avoid static, spark and partial temperature too high, thereby crushing process is comparatively safe.Fluid medium has good immersional wetting to material, can significantly reduce the particulate surface energy, reduces the required stress that ruptures; And from the process of particle fracture, according to the crack propagation condition, the fluid medium molecular adsorption can reduce the required external stress of crack propagation at fresh surface, promotes the expansion of crackle, and prevents the closed again of newborn crackle.If water medium; The aquation of material and water (water-swelling) effect reduces material grains volumetric expansion, hardness, reduces depolymerization and disperses required surging force; The positively charged ion aquation break away to form diffusion double layer and strengthens depolymerization and disperse between the particle nanometer layer, realization and separate impurities and obtain purification.The adding of medicament, the generation foam breaks and has encircled hydration and positively charged ion diffusion double layer, therefore, except that introducing impurity and damaging the environment, has checked depolymerization, the reduction dispersion effect of material grains on the contrary, and the purpose that separation is purified is difficult to realize.The present invention makes full use of the PAL material in water medium camber dispersive natural endowment property characteristics, and employing water is that fluid medium, no medicament add, and integrates flow process reasonableness, non-secondary pollution and resources circulation economy characteristic in one, prepares high-purity PAL material.
The raw material of PAL material is the sedimentary natural nonmetal silicates mineral of marine facies (semiclosed salty lake), is polar material, meets water the hydration swelling effect can take place, and gets into formation diffusion double layer in back in the water, further expands, and makes the mineral volume increase 8-20 doubly.Hydration weakens and has destroyed intergranular connection; Make particle along existing combination vulnerable area (like the set face of uncracked bedding, schistosity, wall reason, mineral grain and the mineral face etc. that dissociates); Form new crack; Make grain breakage, reduce the particulate mechanical strength, pulverize for further flow and reduced energy consumption.
Huge the surface hydration ability and the swelling pressure show that the wettability that the PAL material is good (polarity) makes the hydration of fluid medium be able to give full play to.In addition, between PAL material crystal layer more weak Van der Waals force is only arranged, the aquation of these mineral that are not enough to contend with can, therefore, aquation can take place in PAL material crystal layer and outside surface, the suction of PAL material is prone to expand, legibility leaves under fluid medium.The aquation of compensating cation can (big more, hydroexpansivity is strong more), diffusion double layer thickness (diffusion double layer is thick more, hydration swelling property strong more), (pH value is high more, and surface potential is big more, the enhancing of hydration swelling property for the saltiness of fluid medium pH value; Saltiness is big, and hydration weakens), these factors also affect the aquation disassociation.The wetting ability of PAL material, high aquation can, the high pH value of weak interlayer power and 7.8-9.3, it is disperseed at the fluid medium camber, be to be convenient to depolymerization disperse and separates the natural endowment property characteristic of purifying with basic.
Technical matters based on high-purity fully, the fine PAL material of the high speed flow legal system powder of the no medicament of ydrodynamics principle; Because the hydration swelling that the hydration of high speed flow and material produces and two electric depolymerization power of repelling; Height of materials is disperseed, accomplish miniaturization.Utilize differently, realize separating and purifying with impurity through the spiral centrifugal device with the gravity of impurity.Technological process of the present invention does not have waste gas, discharge of wastewater, and waste residue can be processed as agricultural siliceous fertilizer and macromolecular material strengthening agent WHITE CARBON BLACK, has realized that " environmentally friendly ", resource utilization are close to 100% " resources conservation ".
The present invention uses no medicament high speed flow law technology and depolymerization dispersion and the purification separating technology based on the ydrodynamics principle; The hydration swelling power of having given full play to the hydration of high speed water medium and material and having produced; The dynamic action of the diffusion double layer repulsive force that forms with the abundant aquation of interlayer cation; Promote to disintegrate disperse, separate with impurity and realize purifying (WATER AS FLOW MEDIUM reusable edible), avoided traditional medicament flotation to introduce the harm of impurity atom and contaminate environment; Formulate out high-purity, micro-nano PAL material powder, for manufacturing high-performance, environmental protection flame retardant material provide material foundation.
Specific embodiment described herein only is that the present invention's spirit is illustrated.Person of ordinary skill in the field of the present invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although this paper has used term morely, do not get rid of the possibility of using other term.Using these terms only is in order to describe and explain essence of the present invention more easily; It all is contrary with spirit of the present invention being construed to any additional restriction to them.
Claims (4)
1. a high-performance environment protection type PAL fire retardant material depolymerization purifying technique is characterized in that this technology comprises the steps:
A, depolymerization: adopt target plate formula flow kibbler to carry out depolymerization and disperse; Be that medium carries high-purity PAL material promptly, bump against that material and target plate are in high velocity impact, bump with the fixedly target plate that is provided with the high speed flow; The high-speed functions of flow finally changes the crushing energy of material into, makes material broken;
B, purification: adopt the screw propulsion whizzer to realize purifying; Promptly in screw centrifuge screw rod propelled at high velocity process; Utilize the action of gravity of material particles size; Spiral separates the material of different-grain diameter, and control depolymerization dispersive paste consistency obtains the subparticle less than the different-grain diameter of 100nm-10 μ m.
2. high-performance environment protection type PAL fire retardant material depolymerization purifying technique according to claim 1 is characterized in that, in above-mentioned steps A, the paste consistency after depolymerization disperses is 15%-20%.
3. high-performance environment protection type PAL fire retardant material depolymerization purifying technique according to claim 1 is characterized in that in above-mentioned step B, the rotating speed of screw centrifuge is controlled at 1500r/min-2500r/min.
4. according to claim 1 or 2 or 3 described high-performance environment protection type PAL fire retardant material depolymerization purifying techniques, it is characterized in that the PAL material content in described high-purity PAL material is 90%-98%.
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| CN103641126A (en) * | 2013-12-11 | 2014-03-19 | 甘肃金宇生态环境工程有限公司 | Method for preparing high-performance PAL (phenylalanine ammonia lyase) material by using non-metallic mineral palygorskite |
| CN103783262A (en) * | 2013-12-11 | 2014-05-14 | 甘肃金宇生态环境工程有限公司 | Method for preparing safe and green natural forage material in culture industry |
| CN111592892A (en) * | 2020-04-28 | 2020-08-28 | 山东科技大学 | Method for preparing high-performance PAL material by using non-metallic mineral palygorskite |
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Application publication date: 20120118 |