CN111499781A - Method for producing green environment-friendly polypropylene high-end fiber material - Google Patents
Method for producing green environment-friendly polypropylene high-end fiber material Download PDFInfo
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- CN111499781A CN111499781A CN202010429596.2A CN202010429596A CN111499781A CN 111499781 A CN111499781 A CN 111499781A CN 202010429596 A CN202010429596 A CN 202010429596A CN 111499781 A CN111499781 A CN 111499781A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
Abstract
The invention discloses a method for producing a green environment-friendly polypropylene high-end fiber material, which comprises the following four steps of preparing raw materials, establishing a production line, preparing a polypropylene base material and performing rheological control to produce the green environment-friendly polypropylene high-end fiber material, wherein the material has a melt index of 40-45 g/10min, a yellow index of less than or equal to-1.0, an isotacticity of more than or equal to 95.5%, an ash content of less than or equal to 200 mg/kg and a tensile yield stress of more than or equal to 31 MPa; fish eyes are less than or equal to 10/1520 cm2. The production material of the invention does not contain phthalate, wherein the traditional process is avoided by adding a brand-new non-peroxide degradation agent in the process controlThe defects of the oxide degrading agent solve the problems of easy color change, peculiar smell and the like of the product. In order to further improve the product performance, the material is clearer, the fiber thickness is more uniform, and the hand feeling and the appearance are better by optimizing the additives and the compatibility. The material prepared by the production method can be used as a raw material of melt-blown cloth and used for preparing masks, and the situation that the raw materials for producing medical protective articles are short at present can be greatly relieved.
Description
Technical Field
The invention relates to the technical field of melt-blown fabric materials, in particular to a method for producing a green environment-friendly polypropylene high-end fiber material.
Background
In recent years, the market development of domestic polypropylene fiber materials for non-woven fabrics is fast, particularly high-grade PP fibers such as fine denier, ultra-fine denier, melt-blown non-woven fabrics and other special resins are required to be imported from foreign countries, and the raw materials of the part account for more than 25% of the market. The imported raw materials are mainly used for producing export products, such as masks, sanitary napkins for women, baby diapers and other medical and sanitary products with higher quality requirements. Compared with imported raw materials, the domestic raw materials have the defects of large Melt Flow Rate (MFR) fluctuation, high impurity content, easy color change, peculiar smell and the like, and have serious phenomena of yarn breakage and yarn doubling during production of thin products, thereby affecting the product quality, so that many manufacturers of domestic products are only used for producing low-end products such as carpets, packaging materials and the like.
There are generally two methods for the industrial production of nonwoven fabric fiber materials, hydrogen conditioning and degradation. The hydrogen regulation method is that hydrogen is added in the propylene polymerization process of the fluidized bed reactor to achieve the purpose of adjusting molecular weight by controlling chain transfer, thereby obtaining a product with a target melt index; the degradation method is that the low-melt index polypropylene resin is produced in a fluidized bed reactor as a base material, and a needed melt index product is obtained by selecting a degradation agent and adopting a controllable rheological process. The molecular weight distribution of the product produced by the hydrogen regulation method is relatively wide, when the product is used by downstream manufacturers, the low molecular weight part in the product molecule is easy to generate peculiar smell, and the high molecular weight part forms thicker fibers; the production by the sampling degradation method can overcome some defects of the hydrogen regulation method, but the added degradation agent is generally a peroxide agent, if the type is selected improperly, and factors such as improper process control in the production process and the like easily cause peculiar smell, even stink, color change and the like, and the use of the method in the fields of textile, medicine, health, food and the like is limited.
At present, the industry still uses the degradation process to produce polypropylene fiber materials as the main stream, and the production of high-end fiber materials is finished by taking the optimized high-quality degradation agent as a breakthrough in the process control of the rheology and adding a proper additive through compatibility optimization. However, the current technology still has the following defects:
(1) the selected catalyst has defects;
currently, polypropylene resins are produced mainly as phthalate-containing Ziegler-Natta catalysts, which, although highly active, are plasticizers, identified as a fourth class of toxic chemicals. Research shows that the compound plays a role similar to estrogen in human bodies and animal bodies, can interfere endocrine, and particularly has potential influence on human reproductive systems; meanwhile, the development of human liver, kidney, heart and fetal nervous system are all influenced, so the material containing the substances is listed as a product prohibited from import by some countries.
(2) The product has poor processing performance;
the defects of peculiar smell, broken filaments, thick fibers and the like easily appear in the downstream processing process of the product, which may be related to the selection of the fiber material to be produced by the hydrogen adjusting process. The polypropylene fiber material produced by the hydrogen adjusting process has over-wide molecular weight distribution, the low molecular weight part is easy to volatilize in the processing process to generate special smell, and the mechanical property is reduced to influence the production efficiency; the high molecular weight portion will have stress concentration points to form gel particles, and the drawn fiber is thick, which affects the appearance and can not produce high-end products. On the other hand, although the material is possibly produced by a degradation process, in order to avoid the defects brought to the material by residual and decomposition of peroxide caused by adding a peroxide degradation agent in the process control, the melt index of the base material produced by the fluidized bed reactor is improved, and the purpose of adding less peroxide degradation agent is achieved. However, if the melt index of the reaction base material is increased, the molecular weight distribution of the fiber material is too wide, and the mechanical properties are reduced.
(3) Discoloration (yellowing, or redness) of the article can occur;
the color change of the product is mainly produced by a fiber raw material by a degradation method, a degradation agent selected in the process control is peroxide, when the process parameters are improperly controlled, residue can occur, the residual peroxide is easy to have color change in an acid environment, and the residual peroxide is yellow if the residual peroxide is not properly controlled and is reddish if the residual peroxide is heavy.
(4) The product has strong pungent smell;
the occurrence of a harsh odor in the article is also associated with peroxide degradants selected during the production of the fiber material by the degradation process. In order to reduce the residual peroxide in the fiber material in the industrial production process, some degrading agents with high active oxygen content are selected. The degradation agent of the type has a great defect that if the temperature is too low in the control of the rheological process, the reaction is incomplete, residues occur, and the product cannot reach the expected melt index; if the temperature is too high, the composition will decompose to generate offensive odor, which will affect the use of the product.
(5) The product performance is unstable;
the unstable product performance is mainly shown in the large fluctuation range of the central value of the melt index control, which is related to the improper selection of the process parameters of the base material generated by the fluidized bed reactor or the unstable control on the one hand; on the other hand, to instability of the addition of degradation agents during the control of the flow process. This causes difficulty in controlling the process of producing the product by downstream manufacturers and increases the defective rate.
(6) The product has poor appearance.
In order to avoid the peculiar smell of the fiber material, industrial production enterprises can strive to reduce the residual peroxide degradation agent in the fiber material through process control, so that the addition amount can be relatively controlled; on the other hand, some degradation agents which are not easy to generate peculiar smell are selected, but the degradation agents are generally low in active oxygen content and poor in efficiency, so that the melt index of the produced fiber material is generally not more than 35g/10min, and the aim of producing high-end fiber material is often not achieved. The fiber material with lower melt index has uneven fiber thickness, high hardness, no softness, poor hand feeling and poor aesthetic feeling, and is especially not suitable for producing sanitary products.
Disclosure of Invention
In view of the above, the present invention provides a method for producing a green and environment-friendly polypropylene high-end fiber material, which is free of phthalate, wherein a brand-new non-peroxide degradation agent is added during the process control, so as to avoid the defects of the conventional peroxide degradation agent and solve the problems of color change, odor and the like of the product. In order to further improve the product performance, the material is clearer, the fiber thickness is more uniform, and the hand feeling and the appearance are better by optimizing the additives and the compatibility.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method for producing the green environment-friendly polypropylene high-end fiber material comprises the following steps
S1, preparing raw materials
1) Raw material propylene;
2) nitrogen gas;
3) hydrogen gas;
4) catalyst: phthalate-free CONSISITA C501 novel catalyst;
5) external electron donor: d-9600;
6) and (3) a cocatalyst: triethyl aluminum (TEA);
7) antioxidant: irganox 1010;
8) a stabilizer: irgafox 168;
9) acid scavenger: hydrotalcite;
10) a degradation agent: IRGATEC CR 76, respectively;
11) nucleating agent: HPN-900 Ei;
12) a slipping agent: erucamide, purity requirement 98%;
s2, establishing a production line: a production line for producing green environment-friendly polypropylene high-end fiber materials;
s3 preparation of Polypropylene base stock
1) Introducing raw material propylene into a degassing tower, removing at least carbon monoxide, carbon dioxide and oxygen, discharging from the top of the tower, cooling the propylene led out from the bottom of the tower, introducing the propylene into a desulfurization and deoxidation bed and a drying bed, further removing sulfur, water and the like, finishing refining the propylene to meet the requirement of polymerization-grade purity, pressurizing by using a high-speed pump, and injecting into a fluidized bed reactor;
2) pressurizing high-purity hydrogen and nitrogen by using a hydrogen compressor and a nitrogen compressor respectively, and injecting the pressurized hydrogen and nitrogen into a fluidized bed reactor to establish reaction initiation conditions;
3) the catalyst is pumped into the fluidized bed reactor by a screw pump, the external electron donor is injected into the fluidized bed reactor by a first metering pump to adjust the isotacticity of the product, and the cocatalyst is injected into the fluidized bed reactor by a second metering pump to activate the catalyst; after the conditions of the fluidized bed reactor are established, the external electron donor and the cocatalyst are simultaneously added into the fluidized bed reactor, and then the catalyst is injected, and the reaction is immediately initiated to generate the target polypropylene powder base material;
4) intermittent discharge is adopted in the fluidized bed reactor; the polypropylene base material discharged from the fluidized bed reactor is conveyed into a degassing bin through a discharging system in a dense phase conveying mode, unreacted propylene gas is removed from powder, and the unreacted propylene gas is recycled.
S4, rheology control
1) And (3) after removing propylene gas, the base material in the degassing bin enters a spiral mixing feeder by using a rotary feeder, and additives required by the granulation process are added into the spiral mixing feeder: adding the antioxidant, the stabilizer and the acid scavenger into the spiral mixing feeder by adopting a first weightlessness weighing scale respectively;
2) the required auxiliaries are: respectively premixing a degrading agent, a nucleating agent and a slipping agent with powder, and then uniformly, stably and accurately adding the powder into a spiral mixing feeder by respectively adopting a first weightlessness weighing scale;
3) mixing the additives, the auxiliaries and the base materials added in the spiral mixing feeder into a master batch, adding the master batch into a feeding tank of a granulator set, and feeding the master batch into a mixing roll;
4) and the melt which is fully degraded to achieve the target melt index enters a granulator for underwater granulation, then desalted water is used for conveying the melt to a centrifugal machine for drying, and a classifying screen is used for separating large and small particles, and then the separated particles are conveyed to a storage bin by a fan for packaging and selling.
The invention is comparable to the prior artMore specifically, as can be seen from the above technical solutions, raw materials are prepared through S1; s2, establishing a production line; s3, preparing a polypropylene base material; s4, performing rheological control to produce the green environment-friendly polypropylene high-end fiber material, wherein the material has the following characteristics: the melt index is 40-45 g/10min, the yellow index is less than or equal to-1.0, the isotacticity is greater than or equal to 95.5%, the ash content is less than or equal to 200 mg/kg, and the tensile yield stress is greater than or equal to 31 MPa; fish eyes are less than or equal to 10/1520 cm2。
Particularly, the material is produced by using a phthalate-free catalyst, wherein a brand-new non-peroxide degradation agent IRGATEC CR 76 is added in the process of flow control, so that the defects of the traditional degradation agent are thoroughly overcome, and the problems of easy color change, peculiar smell and the like of the product are solved. The product has lower VOC, lower oligomer content and trace additive residue, and is a brand-new green environment-friendly product.
Furthermore, the non-peroxide degradation agent IRGATEC CR 76 selected by the material is granular, does not react at low temperature, does not need special storage conditions, can be safely and stably used for production and storage, and avoids the fire risk of the traditional peroxide in use.
The material is optimally selected from a degrading agent IRGATEC CR 76 and a nucleating agent HPN-900Ei, the compatibility is optimized, the defects of easy color change, peculiar smell, unstable quality and the like of fiber products are overcome, the material is clearer, the fiber thickness is more uniform, the color is stable, the hand feeling and the impression are greatly improved, and the long-acting thermal stability is good, so the material can be widely applied to the fields of medical protection, personal hygiene products, water purification filtering materials, oil absorption materials and the like.
The material has narrow molecular weight distribution, and the prepared non-woven fabric has no peculiar smell, excellent barrier filtering property, water resistance, air permeability, oil absorption, hydrostatic pressure resistance and high heat-resisting temperature, thinner and more uniform fiber materials, and improved mechanical properties (such as toughness and elongation), thereby being an ideal material for manufacturing medical protective articles.
The material can be used as a melt-blown fabric raw material, and can greatly relieve the situation of shortage of raw materials for producing medical protective articles at present. And the material has higher relative melt index, good fluidity and high extrusion speed in the field of fiber materials, and can effectively improve the production efficiency of downstream manufacturers and reduce the power consumption.
To more clearly illustrate the structural features and effects of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Drawings
FIG. 1 is a flow chart of a method of manufacturing an embodiment of the present invention.
FIG. 2 is a block diagram of a production line according to an embodiment of the present invention.
The attached drawings indicate the following:
1. degassing tower 2, desulfurization deoxidation bed
3. Drying bed 4, high-speed pump
7. Fluidized bed reactor 8, hydrogen compressor
9. Nitrogen compressor 10, screw pump
11. First metering pump 12 and second metering pump
13. Degassing bin 14 and rotary feeder
15. Spiral mixing feeder 16, first weightless weigher
17. Additive premixer 18 and second weightless weighing scale
19. Granulator unit 20 and granulator
21. Centrifuge 22, classifying screen
23. Fan 24, feed bin.
Detailed Description
Examples
A method for producing a green environment-friendly polypropylene high-end fiber material is shown in figure 1 and comprises the following steps:
s1, preparing raw materials.
And S2, establishing a production line.
S3, preparing polypropylene base stock.
And S4, rheology control.
Wherein, the prepared raw materials comprise raw materials of propylene, nitrogen, hydrogen, catalyst, degradation agent, nucleating agent, additive, slipping agent and the like.
1) Raw material propylene with the purity of more than 99.65 percent passes through a degassing tower 1, a desulfurization and deoxidation bed 2 and a drying bed 3 to remove impurities. The purity of the propylene is required to reach more than 99.95 percent of polymerization level for polymerization reaction, and the oxygen content, the sulfur content and the carbon dioxide content are all less than 1.0ppm, the water content is less than 2 ppm, and the carbon monoxide is less than 0.1 ppm.
2) In the reaction polymerization process, nitrogen with the purity of more than 99.99 percent is applied, and the total pressure of the fluidized bed reactor 7 is controlled; the hydrogen with the purity of more than 99.95 percent is used as a chain transfer agent of the molecular weight in the polymerization process.
3) The polymerization reaction is preferably carried out by using a phthalate-free CONSISITA C501 novel catalyst produced by Grace company in America and a matched external electron donor D-9600, so that the environment-friendly base material produced by the reaction is ensured, the activity is very high, and the trace amount of residual ash in the produced base material is ensured.
4) A brand-new hindered hydroxylamine ester degrading agent IRGATEC CR 76 is selected in the control of the granulation rheological process, and the content of active substances is more than 99 percent.
5) The latest nucleating agent Milliken Hyperform produced by America Milliken company, a manufacturer of internationally known nucleating agent, was selected for controlling the rheological process of granulation.
6) In addition to the addition of additives in the control of granulation rheology process, the slipping agent erucamide is added, and the purity requirement is 98%.
S2, establishing a production line: as shown in fig. 2, the production line includes a degassing tower 1, a desulfurization and deoxidation bed 2, a drying bed 3, a high-speed pump 4, a fluidized bed reactor 7, a hydrogen press 8, a nitrogen press 9, a screw pump 10, a first metering pump 11, a second metering pump 12, a degassing bin 13, a rotary feeder 14, a screw mixing downer 15, a first weightlessness metering scale 16, an additive pre-mixer 17, a second weightlessness metering scale 18, a granulator unit 19, a granulator 20, a centrifuge 21, a classifying screen 22, and the like.
Wherein, the degassing tower 1 is connected with a desulfurization and deoxidation bed 2, the desulfurization and deoxidation bed 2 is connected with a drying bed 3, the raw material propylene is introduced into the degassing tower 1, the desorbed carbon monoxide, carbon dioxide, oxygen and the like enter the desulfurization and deoxidation bed 2 and the drying bed 3 to finish refining, and the purity of the propylene reaches the requirement of polymerization grade. The drying bed 3 is communicated with the fluidized bed reactor 7 through the high-speed pump 4, and high-purity propylene is pressurized by the high-speed pump 4 and then injected into the fluidized bed reactor 7.
The fluidized bed reactor 7 is connected with a hydrogen press 8 and a nitrogen press 9, and the hydrogen press 8 and the nitrogen press 9 are used for pressurizing high-purity hydrogen and nitrogen and injecting the pressurized high-purity hydrogen and nitrogen into the fluidized bed reactor 7 to establish reaction initiation conditions. And the fluidized bed reactor 7 is also connected with a screw pump 10, and the screw pump 10 is used for pumping the catalyst into the fluidized bed reactor 7. The fluidized bed reactor 7 is also connected with a first metering pump 11 and a second metering pump 12. The first metering pump 11 is used for injecting the external electron donor D-9600 into the fluidized bed reactor 7 to adjust the product isotacticity, and the second metering pump 12 is used for injecting the cocatalyst into the fluidized bed reactor 7 to activate the catalyst.
The fluidized bed reactor 7 is connected with a degassing bin 13, and the polypropylene base material discharged from the fluidized bed reactor 7 is conveyed into the degassing bin 13 through a discharge system in a dense phase conveying mode, so that unreacted propylene gas is removed from powder and recycled.
The degassing bin 13 is connected to a spiral mixing blanking device 15 through a rotary feeder 14, and the base material in the degassing bin 13 is subjected to propylene gas removal and then enters the spiral mixing blanking device 15 through the rotary feeder 14 by accurately controlling the set load. The spiral mixing feeder 15 is provided with a first weightless weighing scale 16, and the first weightless weighing scale 16 accurately controls the adding amount of additives (antioxidant, stabilizer, acid scavenger) according to the ratio (concentration) according to the load of the rotary feeder 14 and sends the additives to the spiral mixing feeder 15.
And a pipeline special for collecting powder is led out from the upper part of the rotary feeder 14 at the bottom of the degassing bin 13 and enters the additive premixer 17, the powder is collected intermittently, the powder, the degrading agent, the nucleating agent and the slipping agent are premixed in the additive premixer 17 respectively according to the proportion of the powder, and then are put into respective feeding tanks, and a second weightlessness measuring scale 18 is adopted to control the feeding into the spiral mixing feeder 15 according to the load of the rotary feeder 14 according to the ratio (concentration).
The spiral mixing feeder 15 is connected with a granulator unit 19, and a granulator 20, a centrifuge 21, a classifying screen 22, a fan 23 and a storage bin 24 are sequentially arranged behind the output of the granulator unit 19. The melt which is fully degraded to achieve the target melt index enters a granulator 20 for underwater granulation, then desalted water is used for conveying to a centrifuge 21 for drying, and a grading sieve 22 is used for separating particles and then a fan 23 is used for inputting to a storage bin 24 for packaging and selling.
Based on the above production line, the polypropylene base stock preparation step S3 of the present invention can be performed as follows.
S3 preparation of base stock
1) Introducing raw material propylene into a degassing tower 1, controlling the temperature of a tower kettle to be 53-55 ℃, the temperature of a tower top to be 46-48 ℃ and the tower pressure to be 2.10-2.15 MPa, discharging the desorbed carbon monoxide, carbon dioxide, oxygen and the like from the tower top, cooling the propylene led out from the tower kettle to be 35-40 ℃, then introducing the propylene into a desulfurization and deoxidation bed 2 and a drying bed 3, further removing sulfur, water and the like, refining the propylene to meet the requirement of polymerization grade purity, pressurizing by using a high-speed pump 4, and injecting into a fluidized bed reactor 7.
2) High-purity hydrogen and nitrogen are pressurized by a hydrogen compressor 8 and a nitrogen compressor 9 respectively and then injected into a fluidized bed reactor 7 to establish reaction initiation conditions. Controlling the total pressure of the fluidized bed reactor 7 to be 3.15-3.20 MPa and the reaction temperature: 67.5 ℃ to 68.5 ℃ and propylene partial pressure: 2.65 MPa to 2.75MPa, hydrogen to propylene ratio: 0.0095-0.0100 (molar ratio);
3) pumping the optimized CONSISITA C501 catalyst into a fluidized bed reactor 7 by a screw pump 10, and controlling the flow at 2.50-2.75 kg/h; an external electron donor D-9600 matched with the catalyst is injected into a fluidized bed reactor 7 by a first metering pump 11 to adjust the isotacticity of the product, and the flow is controlled to be 3.20-3.50 kg/h; and a cocatalyst of triethyl aluminum TEA is injected into the fluidized bed reactor 7 by a second metering pump 12 to activate the catalyst, and the flow rate is controlled to be 3.7-3.9 kg/h. In the production, the adding amount of the catalyst is kept stable, and the cocatalyst triethyl aluminum is added according to the molar ratio of aluminum to titanium in triethyl aluminum and the catalyst CONSISITA C501, wherein the aluminum/titanium ratio is = 45-50; the external electron donor is added according to the molar ratio of aluminum to silicon in triethyl aluminum and the external electron donor D-9600, wherein the aluminum/silicon = 2.5-2.8.
After the conditions of the fluidized bed reactor 7 are well established, simultaneously adding an external electron donor and a cocatalyst according to the requirements, then injecting an optimal catalyst, and immediately initiating a reaction to generate a target polypropylene powder base material, wherein the melt index is 2.5-3.0 g/10min, and the xylene soluble substance is 3.4-3.6%; when the flow rate of the catalyst is controlled to be 2.50-2.75 kg/h, the capacity of the polypropylene base material generated by the fluidized bed reactor 7 can reach 35.5-37.5 t/h;
4) intermittent discharge is adopted in the fluidized bed reactor 7, the quality of the powder produced in the bed layer is controlled to be kept at 35.5-37.5 t, the discharge is carried out once when the fluidized bed reactor is ultrahigh, 1.2-1.4 t of powder is discharged each time, the residence time of the catalyst in the fluidized bed reactor 7 is strictly controlled to be not more than 1.2h, so that the large change of the melt index range caused by the base material generated by the aging of the catalyst is avoided, the molecular weight of the base material is respectively too wide, and the ratio of the low molecular weight to the high molecular weight is too.
The polypropylene base material discharged from the fluidized bed reactor 7 is conveyed into a degassing bin 13 in a dense phase conveying mode through a discharging system, unreacted propylene gas is removed from powder, and the unreacted propylene gas is recycled.
S4 rheology control
1) After removing propylene gas from the base material in the degassing bin 13, accurately controlling the load of 35.5-37.5 t/h by using a rotary feeder 14, feeding the base material into a spiral mixing blanking device 15, and accurately adding an additive required in the granulation process, namely an antioxidant Irganox 1010, a stabilizer Irgafox 168 and an acid scavenger hydrotalcite, into the spiral mixing blanking device 15 by respectively adopting respective first weightlessness weighing scales 16 (respectively referring to an antioxidant weightlessness weighing scale, a stabilizer weightlessness weighing scale and an acid scavenger weightlessness weighing scale) according to the load of the rotary feeder 14 according to the ratio (concentration), wherein the added antioxidant Irganox 1010: 300 to 500 ppm; stabilizer Irgafox 168: 500 to 800 ppm; acid scavenger hydrotalcite: 200 to 300 ppm. All additives and the base material can be uniformly mixed in the spiral mixing feeder 15, so that the product performance can obtain expected requirements in the granulation process;
2) in order to ensure that the preferred degradation agent IRGATEC CR 76, the nucleating agent HPN-900Ei and the slipping agent erucamide can be uniformly, stably and accurately added into the spiral mixing downer 15, a pipeline specially used for collecting powder is led out from the upper part of the rotary feeder 14 at the bottom of the degassing bin 13 and enters the additive premixer 17, by intermittently collecting powder, according to the proportion of 2:1 of the powder to the degradation agent, the nucleating agent and the slipping agent, respectively pre-mixing in an additive pre-mixer 17, then putting into respective feeding tanks (respectively a degradation agent feeding tank, a nucleating agent feeding tank and a slipping agent feeding tank), and (2) adding the mixture into a spiral mixing feeder 15 by using a corresponding second weightlessness measuring scale 18 (respectively a degrading agent weightlessness measuring scale, a nucleating agent weightlessness measuring scale and a slipping agent weightlessness measuring scale) according to the load of the rotary feeder 14 in a ratio (concentration), wherein the weight ratio of the degrading agent IRGATEC CR 76 added into the base material: 5000-8000 ppm; nucleating agent HPN-900 Ei: 200-300 ppm; the slipping agent erucamide: 1200 to 1500 ppm. Uniformly mixing the mixture with a base material in a spiral mixing feeder 15 to ensure that a product with stable melt index can be obtained in the rheological process control of the granulation process;
3) the master batch prepared by mixing the additives, the auxiliaries and the base materials added in the spiral mixing feeder 15 is added into a feeding tank of a granulator set 19 and then enters a mixing roll; gradually increasing the temperature of the barrel of the unit to be more than 250 ℃ in the process of entering the mixing roll so as to ensure that the added degrading agent IRGATEC CR 76 can fully exert the efficiency of the barrel and obtain a product with narrow molecular weight distribution, low volatile content and a melt index of 40-45 g/10 min;
4) the melt which is fully degraded to achieve the target melt index enters a granulator 20 for underwater granulation, then desalted water is used for conveying to a centrifuge 21 for drying, and a grading sieve 22 is used for separating particles and then a fan 23 is used for inputting to a storage bin 24 for packaging and selling.
The green environment-friendly polypropylene high-end fiber material produced by the method has the main advantages as shown in the following table 1:
the material is prepared from novel catalysts, additives and other raw materials, particularly does not contain phthalate, adopts non-peroxide as the selected degradation agent, thoroughly avoids the defects of the traditional degradation agent, has lower VOC, lower oligomer content and trace additive residue, and is a brand-new green and environment-friendly product.
The non-peroxide degradation agent selected by the material is granular, does not react at low temperature, does not need special storage conditions, can be safely and stably used for production and storage, and avoids the ignition risk of the traditional peroxide in use.
The material solves the defects of easy color change, peculiar smell, unstable quality and the like of fiber products by optimizing the compatibility of the degrading agent and the nucleating agent, and ensures that the material is clearer, the fiber thickness is more uniform, the color is stable, the hand feeling and the impression are greatly improved, and the long-acting thermal stability is good, so the material can be widely applied to the fields of medical protection, personal hygiene products, water purifying and filtering materials, oil absorbing materials and the like.
The material has narrow molecular weight distribution, and the prepared non-woven fabric has no peculiar smell, excellent barrier filtering property, water resistance, air permeability, oil absorption, hydrostatic pressure resistance and high heat-resisting temperature, thinner and more uniform fiber materials, and improved mechanical properties (such as toughness and elongation), thereby being an ideal material for manufacturing medical protective articles.
The material can be used as a melt-blown fabric raw material, and can greatly relieve the situation of shortage of raw materials for producing medical protective articles at present.
The material has higher relative melt index in the field of fiber materials, good fluidity and high extrusion speed, and can effectively improve the production efficiency of downstream manufacturers and reduce the power consumption.
Application example
Taking a project of 30 ten thousand tons/year propane dehydrogenation for preparing high-performance propylene by using giant positive science and technology limited of Dongguan as an example, the process of preparing the base material has the following parameters: 1) the temperature of a tower kettle of a degassing tower 1 is 54 ℃, the temperature of a tower top is 47 ℃, and the tower pressure is 2.13 MPa; the propylene drawn out from the bottom of the column was cooled to 38 ℃. 2) Total pressure of fluidized bed reactor 7 of 3.188MPa, reaction temperature: 68.0 ℃, propylene partial pressure: 2.70MPa, hydrogen to propylene ratio: 0.00988 (molar ratio). 3) The catalyst is pumped into the reactor by a screw pump 10 with the control flow rate of 2.60 kg/h; the external electron donor is injected into the reactor to control the flow rate to be 3.25 kg/h; the cocatalyst injection control flow rate is 3.8 kg/h. The molar ratio of the aluminum and titanium content in the cocatalyst and the catalyst aluminum/titanium = 48; the molar ratio of the aluminium and silicon content in the cocatalyst and the external electron donor aluminium/silicon = 2.7. 4) The fluidized bed reactor 7 initiates a reaction to generate a target polypropylene powder base material, wherein the melt index is 2.8g/10min, and the xylene soluble substance is 3.5 percent; when the catalyst flow rate is controlled at 2.60kg/h, the polypropylene base capacity generated in the fluidized bed reactor 7 reaches 36.5 t/h. 5) The fluidized bed reactor 7 adopts intermittent discharge, the quality of the powder produced in the bed layer is controlled to be kept at 36.5t, when the fluidized bed reactor is ultrahigh, the discharge is carried out once, 1.3t of the powder is discharged each time, and the retention time of the catalyst in the fluidized bed reactor 7 is strictly controlled not to exceed 1.2 h.
The process setting parameters of the rheological control process are as follows: 1) after removing propylene gas, the base material in the degassing bin 13 enters a spiral mixing feeder 15 by using a rotary feeder 14 to accurately control the load of 36.5t/h, and additives required in the granulation process are added into the spiral mixing feeder 15, wherein the added antioxidant: 400 ppm; a stabilizer: 650 ppm; acid scavenger: 250 ppm. 2) The powder is collected intermittently, and the powder, the degrading agent, the nucleating agent and the slipping agent are premixed in a premixer according to the ratio of 2:1 and are added into a spiral mixing feeder 15, wherein the degrading agent is added into a base material: 65000 ppm; nucleating agent: 150 ppm; the slipping agent erucamide: 1400 ppm.
The main advantages of the green environment-friendly polypropylene high-end fiber material (typical product) prepared by the method are shown in the following table 2.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (10)
1. A method for producing green environment-friendly polypropylene high-end fiber material is characterized by comprising the following steps: comprises the following steps
S1, preparing raw materials
1) Raw material propylene;
2) nitrogen gas;
3) hydrogen gas;
4) catalyst: phthalate-free CONSISITA C501 novel catalyst;
5) external electron donor: d-9600;
6) and (3) a cocatalyst: triethyl aluminum (TEA);
7) antioxidant: irganox 1010;
8) a stabilizer: irgafox 168;
9) acid scavenger: hydrotalcite;
10) a degradation agent: IRGATEC CR 76, respectively;
11) nucleating agent: HPN-900 Ei;
12) a slipping agent: erucamide, purity requirement 98%;
s2, establishing a production line: a production line for producing green environment-friendly polypropylene high-end fiber materials;
s3 preparation of Polypropylene base stock
1) Introducing raw material propylene into a degassing tower, removing at least carbon monoxide, carbon dioxide and oxygen, discharging from the top of the tower, cooling the propylene led out from the bottom of the tower, introducing the propylene into a desulfurization and deoxidation bed and a drying bed, further removing sulfur, water and the like, finishing refining the propylene to meet the requirement of polymerization-grade purity, pressurizing by using a high-speed pump, and injecting into a fluidized bed reactor;
2) pressurizing high-purity hydrogen and nitrogen by using a hydrogen compressor and a nitrogen compressor respectively, and injecting the pressurized hydrogen and nitrogen into a fluidized bed reactor to establish reaction initiation conditions;
3) the catalyst is pumped into the fluidized bed reactor by a screw pump, the external electron donor is injected into the fluidized bed reactor by a first metering pump to adjust the isotacticity of the product, and the cocatalyst is injected into the fluidized bed reactor by a second metering pump to activate the catalyst; after the conditions of the fluidized bed reactor are established, the external electron donor and the cocatalyst are simultaneously added into the fluidized bed reactor, and then the catalyst is injected, and the reaction is immediately initiated to generate the target polypropylene powder base material;
4) intermittent discharge is adopted in the fluidized bed reactor; the polypropylene base material discharged from the fluidized bed reactor is conveyed into a degassing bin through a discharging system in a dense phase conveying mode, unreacted propylene gas is removed from powder, and the unreacted propylene gas is recycled;
s4, rheology control
1) And (3) after removing propylene gas, the base material in the degassing bin enters a spiral mixing feeder by using a rotary feeder, and additives required by the granulation process are added into the spiral mixing feeder: adding the antioxidant, the stabilizer and the acid scavenger into the spiral mixing feeder by adopting a first weightlessness weighing scale respectively;
2) the required auxiliaries are: respectively premixing the degrading agent, the nucleating agent and the slipping agent with the powder, and then uniformly, stably and accurately adding the powder into a spiral mixing feeder by respectively adopting a second weightlessness weighing scale;
3) mixing the additives, the auxiliaries and the base materials added in the spiral mixing feeder into a master batch, adding the master batch into a feeding tank of a granulator set, and feeding the master batch into a mixing roll;
4) and the melt which is fully degraded to achieve the target melt index enters a granulator for underwater granulation, then desalted water is used for conveying the melt to a centrifugal machine for drying, and a classifying screen is used for separating large and small particles, and then the separated particles are conveyed to a storage bin by a fan for packaging and selling.
2. The method for producing green environment-friendly polypropylene high-end fiber material as claimed in claim 1, wherein: in step S3, in step 1), the degassing tower controls the temperature of a tower kettle to be 53-55 ℃, the temperature of a tower top to be 46-48 ℃ and the pressure of the tower to be 2.10-2.15 MPa, and carbon monoxide, carbon dioxide and oxygen are removed; and cooling the propylene led out from the tower kettle to 35-40 ℃, and then feeding the propylene into a desulfurization and deoxidation bed and a drying bed to remove sulfur and water.
3. The method for producing green environment-friendly polypropylene high-end fiber material as claimed in claim 1, wherein: in step S3, 2), hydrogen and nitrogen are injected, the total pressure of the fluidized bed reactor is controlled to be 3.15 to 3.20MPa, and the reaction temperature is controlled to be: 67.5 ℃ to 68.5 ℃ and propylene partial pressure: 2.65 MPa-2.75 MPa, hydrogen and propylene molar ratio: 0.0095-0.0100.
4. The method for producing green environment-friendly polypropylene high-end fiber material as claimed in claim 1, wherein: in step S3, pumping the catalyst into the fluidized bed reactor by a screw pump, and controlling the flow rate to be 2.50-2.75 kg/h; injecting an external electron donor into the fluidized bed reactor by using a first metering pump, and controlling the flow rate to be 3.20-3.50 kg/h; and injecting the cocatalyst into the fluidized bed reactor by using a second metering pump, and controlling the flow rate to be 3.7-3.9 kg/h.
5. The method for producing green environment-friendly polypropylene high-end fiber material as claimed in claim 4, wherein: in the production, the adding amount of the catalyst is kept stable, and the cocatalyst is added according to the molar ratio of aluminum to titanium = 45-50 of the cocatalyst to the content of aluminum and titanium in the catalyst; the external electron donor is added according to the molar ratio of aluminum to silicon in the cocatalyst to the external electron donor, wherein the aluminum/silicon = 2.5-2.8.
6. The method for producing green environment-friendly polypropylene high-end fiber material as claimed in claim 1, wherein: in step S3, initiating a reaction in a fluidized bed reactor to generate a target polypropylene powder base material, wherein the melt index is 2.5-3.0 g/10min, and the xylene soluble is 3.4-3.6%; when the flow rate of the catalyst is controlled to be 2.50-2.75 kg/h, the capacity of the polypropylene base material generated by the fluidized bed reactor reaches 35.5-37.5 t/h.
7. The method for producing green environment-friendly polypropylene high-end fiber material as claimed in claim 1, wherein: in step S3, intermittent discharging is adopted in the fluidized bed reactor, the quality of the powder produced in the bed layer is controlled to be kept at 35.5-37.5 t, discharging is carried out once when the bed layer is ultrahigh, 1.2-1.4 t of powder is discharged each time, and the retention time of the catalyst in the fluidized bed reactor is strictly controlled not to exceed 1.2 h.
8. The method for producing green environment-friendly polypropylene high-end fiber material as claimed in claim 1, wherein: in step S4, after removing propylene gas, the base material in the degassing bin enters a spiral mixing feeder by using a rotary feeder to accurately control the load of 35.5-37.5 t/h, and the addition amount of each additive is as follows: antioxidant: 300 to 500 ppm; a stabilizer: 500 to 800 ppm; acid scavenger: 200-300 ppm, and all additives and the base material can be uniformly mixed in the spiral feeder.
9. The method for producing green environment-friendly polypropylene high-end fiber material as claimed in claim 1, wherein: leading a pipeline special for collecting powder from the upper part of a rotary feeder at the bottom of a degassing bin to enter an additive premixer, intermittently collecting the powder, premixing the powder in the premixer according to the ratio of the powder to a degrading agent, a nucleating agent and a slipping agent being 2:1, then putting the powder into respective feeding tanks, and adding the powder into a spiral mixing feeder according to the load of the rotary feeder and the concentration ratio by adopting a second weightlessness measuring scale; adding a degrading agent into the base material: 5000-8000 ppm; nucleating agent: 200-300 ppm; a slipping agent: 1200-1500 ppm, and uniformly mixing with the base material in a spiral feeder.
10. The method for producing green environment-friendly polypropylene high-end fiber material as claimed in claim 1, wherein: the produced green environment-friendly polypropylene high-end fiber material has the following material characteristics: the melt index is 40-45 g/10min, the yellow index is less than or equal to-1.0, the isotacticity is greater than or equal to 95.5%, the ash content is less than or equal to 200 mg/kg, and the tensile yield stress is greater than or equal to 31 MPa; fish eyes are less than or equal to 10/1520 cm2。
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