CN110054912A - A kind of method and product being pyrolyzed preparation high level gum filler based on shrimp crab based shell - Google Patents
A kind of method and product being pyrolyzed preparation high level gum filler based on shrimp crab based shell Download PDFInfo
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- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention belongs to gum fillers to prepare correlative technology field, and disclose a kind of method for being pyrolyzed preparation high level gum filler based on shrimp crab based shell comprising: shrimp and crab shells pretreatment；It is pyrolyzed shell powder sample preparation pyrolytic carbon；Cleaning, drying and the milled processed of pyrolytic carbon.Wherein pass through the design to reaction partner and pyrolytic process route, it can be ensured that obtain the calcium carbonate granule of Nano grade, while by and the combination of organic principle improve the high rigidity and high tenacity of filler.In addition, special auxiliary agent is added in the present invention in pyrolytic carbon last handling process, actual test shows that the performances such as rigidity, tensile strength, permeability, anti-flammability and the heat resistance of rubber can be promoted.The invention also discloses corresponding gum filler products.Present invention process process is relatively easy, and reaction condition is easy to regulate and control, and preparation cost is lower, and can reduce environmental pollution caused by the throwing aside of shrimp and crab shells, and realizes resource utilization.
Description
Technical field
The invention belongs to gum fillers to prepare correlative technology field, be based on shrimp crab base enclosure body heat more particularly, to one kind
The method and product of solution preparation high level gum filler.
Background technique
It is well known that calcium carbonate is widely used in rubber, plastics, papermaking as one of most important inorganic filler
Etc. industries.Influence of the gum filler to the mechanical performance of polymer depend primarily on they partial size, shape, surface characteristic and point
The degree of dissipating.For calcium carbonate, the greatest problem as gum filler is hydrophily, this will lead to itself and polymer substrate interface
In conjunction with inhomogeneities and dispersion inhomogeneities, to influence the mechanical performance of material.Since pure calcium carbonate granule is poly-
Dispersibility in polymer matrix is poor, therefore numerous studies personnel are modified using the preferable coupling agent of hydrophobicity or reactive surfaces
Agent carries out surface organic modification to calcium carbonate by the method for absorption or Surfacecoating, to improve its dispersing characteristic.
For example, patent of invention CN106830043A disclose it is a kind of by aluminate coupling agent, silane, lauric acid, nonionic
Type surfactant compound is modifying agent, and in the method for this surface modified nano calcium carbonate；For another example, patent of invention
CN104084059A discloses one kind using one or both of oleic acid and stearic acid mixture as modifying agent, is received with hydrophobically modified
The preparation method of the calcium carbonate-filled composite silicone rubber membrane of rice.However, further investigations have shown that, such methods use usually all
It is technical grade calcium carbonate, and needs in modifying process using the higher compound of price, this improves making for pearl filler
Use cost.On the other hand, the modified condition of calcium carbonate is more harsh, and the addition of modifying agent often can band to the performance of polymer
Partially to negatively affect.Correspondingly, this field needs to make this further improvement, wants to meet higher quality and efficiency
The gum filler preparation demand asked.
Summary of the invention
For the above shortcoming and Improvement requirement of the prior art, the present invention provides one kind to be based on shrimp crab base enclosure body heat
The method and product of solution preparation high level gum filler, wherein being gone forward side by side by being specifically chosen shrimp crab based shell as carbonic acid calcium source
One step targeted design matched pyrolytic process route and reaction mechanism, accordingly can be sufficiently by the knot of calcium carbonate and organic matter
It closes to improve the high rigidity and high tenacity of material, while eliminating modification procedure compared with prior art, significantly improve production
Efficiency and product quality.
To achieve the above object, according to one aspect of the present invention, it provides a kind of based on the pyrolysis preparation of shrimp crab based shell
The method of high level gum filler, which is characterized in that this method includes the following steps:
(a) pre-treatment step of shrimp and crab shells
Break process will be carried out after the cleaning of shrimp crab based shell, obtains the shell broken material that average-size is 0.5cm~2cm；
(b) preparation step of target pyrolytic carbon
Shell broken material is put into the reactor for being built-in with heat transfer medium ball, and is pyrolyzed under inert gas protection
Processing, wherein inside reactor temperature is set to 300 DEG C~1000 DEG C, and pyrolysis time is set to 20min~for 24 hours；
In the process, shell broken material is heated is decomposed into semicoke ingredient and volatile matter, and the semicoke ingredient is with described anti-
Answer the lifting blade in device to move together, and by heat transfer medium ball it is continuous percussion and auxiliary heat transfer, while with the volatile matter into
Row cross reaction ultimately generates target pyrolytic carbon；
(c) cleaning, drying and milled processed step of pyrolytic carbon
Step (b) target pyrolytic carbon generated is successively cleaned using organic solvent and deionized water, and is filtered
Obtain clean pyrolytic carbon；This pyrolytic carbon is placed in in 50 DEG C~105 DEG C of baking oven dry certain time, is lower than its moisture content
5%, dry pyrolytic carbon is then placed in grinder and is added auxiliary agent, is fully ground to obtain average grain diameter to be 3 μm~50 μm
Final product, thus to obtain required gum filler product；
Wherein the auxiliary agent is selected from one of following substance or mixture, and its additional amount accounts for the pyrolytic carbon after drying
Quality accounting is 3 ‰~1%: triethanolamine, diglycolamine, 2 hydroxy ethylamine, undecylene aldehyde, polyamide, glycerol, poly- second
Alkene wax, oxidized polyethylene wax, phthalic acid, palmitic acid.
As it is further preferred that preferably taking external heat source to heat the reactor in step (b)；Institute
It states heat transfer medium ball to be preferably sent into after external heating in the reactor, and these heat transfer medium balls are preferably heated to
500 DEG C~1100 DEG C of temperature.
As it is further preferred that including the parents such as alkyl, ester group in target pyrolytic carbon generated in step (b)
The hydrophilic radicals such as oil base group and hydroxyl, carboxyl promote the coupling at polymer substrate interface and calcium carbonate surface by this method, and
The modification process of calcium carbonate can be saved.
As it is further preferred that in step (c), it is preferred to use the mode of ultrasonic cleaning carries out target pyrolytic carbon clear
It washes, and supersonic frequency is set as 30kHz~90kHz, scavenging period is 1h~9h.
As it is further preferred that being fully ground and preferably obtaining average grain diameter afterwards is 25 μm~30 μm in step (c)
Final product.
As it is further preferred that gum filler obtained preferably prepares rubber with the incorporation of 1phr~12phr.
It is another aspect of this invention to provide that additionally providing corresponding high level gum filler product.
As it is further preferred that calcium carbonate partial size is Nano grade, and is not easy in above-mentioned high level gum filler product
Agglomeration occurs.
As it is further preferred that the specific surface area of above-mentioned high level gum filler product is 30m2/ g or more.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit:
1, the present invention, which passes through, introduces shrimp crab based shell as carbonic acid calcium source, and according to the ingredient and architectural characteristic of shrimp and crab shells
Targeted design pyrolytic process route is handled, and thermal decomposition product is pyrolytic carbon rich in nanometer grade calcium carbonate, and is had
The organic group of coupled action mutually should be and prepare high-valued product and provide new technique direction；
2, especially, by the redesign to key parameter and operating procedure in pyrolytic process route, have in pyrolytic carbon
The distribution of machine object causes calcium carbonate to be separated in crystallization process, and the calcium carbonate partial size after crystallization can achieve Nano grade, and
And have good dispersibility in pyrolytic carbon, it is not susceptible to agglomeration；The combination of calcium carbonate and organic matter can guarantee material respectively
The high rigidity and high tenacity of material, so as to improve the scope of application of material；
3, on the other hand, due to the semicoke and volatile matter generation reciprocation during pyrolytic reaction, volatile matter two is come from
The hydroperoxyl radical of secondary response occupies multiclass active site in semicoke, and the organic matters such as chitin, amino acid, lipid is promoted to occur to divide
Solution and reform, while the inorganic component in shrimp shell plays certain catalytic action, in the remaining organic matter ultimately generated containing alkyl,
The hydrophilic radicals such as the lipophilic groups such as ester group and hydroxyl, carboxyl can effectively promote polymer substrate interface and calcium carbonate surface
Coupling；Compared with unmodified nanometer calcium carbonate, pyrolytic carbon eliminates modified step as filler, improves production efficiency, drop
Low production cost.
4, according to shrimp crab bio-rubber filler prepared by the present invention, compared with ordinary calcium carbonate filler, nanoparticle is filled out
The specific surface area of material significantly increases, this is conducive to the strong―binding interface between filler and polymer substrate, and then improved polymerization
Physical performance；In addition, by the way that special auxiliary agent is added in the present invention, actual test shows effectively promote the rigidity of rubber, draw
Stretch the performances such as intensity, permeability, anti-flammability and heat resistance.
Detailed description of the invention
Fig. 1 is the whole work according to the pyrolysis preparation gum filler method constructed by the present invention by taking shrimp crab based shell as an example
Skill flow diagram.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Fig. 1 is the integrated artistic flow diagram according to pyrolysis preparation gum filler method constructed by the present invention.Such as Fig. 1
Shown, the present invention is studied by processing mode, reaction mechanism and the multiple key parameters etc. to entire technical process
And improvement, it is accordingly remarkably improved the quality of final obtained filler product compared with the prior art, is provided simultaneously with reaction condition
It is easy to the advantages that regulating and controlling, is high-efficient, at low cost.In addition, additionally aiding, to effectively reduce environment caused by the throwing aside of shrimp and crab shells dirty
Dye realizes comprehensive utilization of resources.
Basic conception according to the invention, the method for being pyrolyzed preparation high level gum filler based on shrimp crab based shell mainly include
The following steps:
Firstly, being the pre-treatment step of shrimp and crab shells body.
Break process will be carried out after the cleaning of shrimp crab based shell, obtains the shell broken material that average-size is 0.5cm~2cm；
It then, is the preparation step of target pyrolytic carbon.
Shell broken material is put into the reactor for being built-in with heat transfer medium ball, and is pyrolyzed under inert gas protection
Processing, wherein inside reactor temperature is set to 300 DEG C~1000 DEG C, and pyrolysis time is set to 20min~for 24 hours.
In the process, shell broken material is heated is decomposed into semicoke ingredient and volatile matter, and the semicoke ingredient is with described anti-
Answer the lifting blade in device to move together, and by heat transfer medium ball it is continuous percussion and auxiliary heat transfer, while with the volatile matter into
Row cross reaction ultimately generates target pyrolytic carbon.
Finally, being the cleaning, drying and milled processed step of pyrolytic carbon.
Target pyrolytic carbon generated is successively cleaned using organic solvent and deionized water, and is obtained by filtration clean
Pyrolytic carbon；This pyrolytic carbon is placed in in 50 DEG C~105 DEG C of baking oven dry certain time, makes its moisture content lower than 5%, then
Dry pyrolytic carbon is placed in grinder and is added auxiliary agent, is fully ground to obtain the final production that average grain diameter is 3 μm~50 μm
Object, thus to obtain required gum filler product；
Wherein the auxiliary agent is selected from one of following substance or mixture, and its additional amount accounts for the pyrolytic carbon after drying
Mass percent is 3 ‰~1%: triethanolamine, 2 hydroxy ethylamine, undecylene aldehyde, polyamide, glycerol, gathers diglycolamine
Ethylene waxes, oxidized polyethylene wax, phthalic acid, palmitic acid.
It below will be by some specific embodiments, more clearly to illustrate the present invention.
Embodiment 1
(1) shell pre-processes: after cleaning shrimp shell with clear water, carrying out break process to it, obtains partial size 0.5~1cm's
Shell powder sample；
(2) it is pyrolyzed shell powder sample preparation pyrolytic carbon: the shell powder sample being placed in reactor being heated by external heat source, and is led to
Cross that process control inside reactor temperature is 450 DEG C, heat transfer medium ball temperature is about 570 DEG C, pyrolysis time 8h；Pyrolysis starts
Forward reaction device is passed through excessive inert gas so that air is discharged, and reaction stops ventilation after starting, shell broken material is heated to be decomposed into
Semicoke ingredient and volatile matter, the semicoke ingredient move together with the lifting blade in the reactor, and by heat transfer medium ball
Continuous percussion and auxiliary heat transfer, while interacting and reacting with the volatile matter, ultimately generate target pyrolytic carbon；
(3) cleaning treatment of pyrolytic carbon: being attached to a small amount of tar of pyrolysis carbon surface using organic solvent cleaning first, then
The residual organic solvents of pyrolysis carbon surface are cleaned using deionized water；Cleaning process carries out on supersonic wave cleaning machine, and frequency is
30kHz, scavenging period are 9h；
(4) drying and milled processed of pyrolytic carbon: filtering cleaning agent obtains clean pyrolytic carbon, pyrolytic carbon is placed in 105
DEG C baking oven in, it is dry after its moisture content be lower than 2%；Dry pyrolytic carbon is placed in grinder, 3 ‰ triethanolamine is added
After auxiliary agent, it is fully ground 12h and obtains the pyrolytic carbon sample that partial size is 3~6 μm；The filler incorporation controls when as rubber compounding
For 8phr.
The rubber of incorporation pyrolysis carbon filler in embodiment 1 is tested for the property, density, tensile strength, is pulled apart at hardness
Elongation is shown in Table 1.
1 rubber performance parameter list of table
| Performance indicator | Density | Hardness | Tensile strength | Elongation at break |
| Unit | g/cm3 | Shore A degree | Mpa | % |
| National standard | GB4472-84 | GB/T531-1999 | GB/T528-1998 | GB/T528-1998 |
| Embodiment 1 | 1.65 | 78 | 4.50 | 500 |
Embodiment 2
(1) shell pre-processes: after cleaning shrimp shell with clear water, carrying out break process to it, obtains partial size in the shell of 1~2cm
Powder sample；
(2) it is pyrolyzed shell powder sample preparation pyrolytic carbon: the shell powder sample being placed in reactor being heated by external heat source, and is led to
Cross process control inside reactor temperature be 300 DEG C, heat transfer medium ball temperature is about 500 DEG C, pyrolysis time be for 24 hours；Pyrolysis is opened
Beginning forward reaction device is passed through excessive inert gas so that air is discharged, and reaction stops ventilation after starting, and shell broken material is thermally decomposed
For semicoke ingredient and volatile matter, which moves together with the lifting blade in the reactor, and by heat transfer medium
The continuous percussion and auxiliary heat transfer of ball, while interacting and reacting with the volatile matter, ultimately generate target pyrolytic carbon；
(3) cleaning treatment of pyrolytic carbon: being attached to a small amount of tar of pyrolysis carbon surface using organic solvent cleaning first, then
The residual organic solvents of pyrolysis carbon surface are cleaned using deionized water；Cleaning process carries out on supersonic wave cleaning machine, and frequency is
40kHz, scavenging period are 7h；
(4) drying and milled processed of pyrolytic carbon: filtering cleaning agent obtains clean pyrolytic carbon, pyrolytic carbon is placed in 105
DEG C baking oven in, it is dry after its moisture content be lower than 2%；Dry pyrolytic carbon is placed in grinder, 20 ‰ diethylene glycol (DEG) is added
After amine auxiliary agent, it is fully ground 10h and obtains the pyrolytic carbon sample that partial size is 6~12 μm；Filler incorporation when as rubber compounding
Control is 12phr.
Embodiment 3
(1) shell pre-processes: after cleaning crab shell with clear water, carrying out break process to it, obtains partial size 1~1.5cm's
Shell powder sample；
(2) it is pyrolyzed shell powder sample preparation pyrolytic carbon: the shell powder sample being placed in reactor being heated by external heat source, and is led to
Cross that process control inside reactor temperature is 600 DEG C, heat transfer medium ball temperature is about 660 DEG C, pyrolysis time 5.5h；Pyrolysis is opened
Beginning forward reaction device is passed through excessive inert gas so that air is discharged, and reaction stops ventilation after starting, and shell broken material is thermally decomposed
For semicoke ingredient and volatile matter, which moves together with the lifting blade in the reactor, and by heat transfer medium
The continuous percussion and auxiliary heat transfer of ball, while interacting and reacting with the volatile matter, ultimately generate target pyrolytic carbon；
(3) cleaning treatment of pyrolytic carbon: being attached to a small amount of tar of pyrolysis carbon surface using organic solvent cleaning first, then
The residual organic solvents of pyrolysis carbon surface are cleaned using deionized water；Cleaning process carries out on supersonic wave cleaning machine, and frequency is
50kHz, scavenging period are 5h；
(4) drying and milled processed of pyrolytic carbon: filtering cleaning agent obtains clean pyrolytic carbon, pyrolytic carbon is placed in 105
DEG C baking oven in, it is dry after its moisture content be lower than 2%；Dry pyrolytic carbon is placed in grinder, 80 ‰ 2- hydroxyl is added
After ethamine auxiliary agent, it is fully ground 8h and obtains the pyrolytic carbon sample that partial size is 12~20 μm；The filler mixes when as rubber compounding
Amount control is 9phr.
Embodiment 4
(1) shell pre-processes: after cleaning crab shell with clear water, carrying out break process to it, obtains partial size in the shell of 1~2cm
Powder sample；
(2) it is pyrolyzed shell powder sample preparation pyrolytic carbon: the shell powder sample being placed in reactor being heated by external heat source, and is led to
Cross that process control inside reactor temperature is 710 DEG C, heat transfer medium ball temperature is about 780 DEG C, pyrolysis time 3.5h；Pyrolysis is opened
Beginning forward reaction device is passed through excessive inert gas so that air is discharged, and reaction stops ventilation after starting, and shell broken material is thermally decomposed
For semicoke ingredient and volatile matter, which moves together with the lifting blade in the reactor, and by heat transfer medium
The continuous percussion and auxiliary heat transfer of ball, while interacting and reacting with the volatile matter, ultimately generate target pyrolytic carbon；
(3) cleaning treatment of pyrolytic carbon: being attached to a small amount of tar of pyrolysis carbon surface using organic solvent cleaning first, then
The residual organic solvents of pyrolysis carbon surface are cleaned using deionized water；Cleaning process carries out on supersonic wave cleaning machine, and frequency is
70kHz, scavenging period are 4h；
(4) drying and milled processed of pyrolytic carbon: filtering cleaning agent obtains clean pyrolytic carbon, pyrolytic carbon is placed in 50
DEG C baking oven in, it is dry after its moisture content be lower than 5%；Dry pyrolytic carbon is placed in grinder, 0.1% hendecene is added
After auxiliary agent made of aldehyde is compounded with polyamide, it is fully ground 6h and obtains the pyrolytic carbon sample that partial size is 20~25 μm；As
Filler incorporation control is 6phr when rubber compounding.
Embodiment 5
(1) shell pre-processes: after cleaning the mixture that shrimp, crab shell respectively account for 50% with clear water, carrying out break process to it, obtains
To partial size 0.5~1.5cm shell powder sample；
(2) it is pyrolyzed shell powder sample preparation pyrolytic carbon: the shell powder sample being placed in reactor being heated by external heat source, and is led to
Cross that process control inside reactor temperature is 750 DEG C, heat transfer medium ball temperature is about 800 DEG C, pyrolysis time 1.5h；Pyrolysis is opened
Beginning forward reaction device is passed through excessive inert gas so that air is discharged, and reaction stops ventilation after starting, and shell broken material is thermally decomposed
For semicoke ingredient and volatile matter, which moves together with the lifting blade in the reactor, and by heat transfer medium
The continuous percussion and auxiliary heat transfer of ball, while interacting and reacting with the volatile matter, ultimately generate target pyrolytic carbon；
(3) cleaning treatment of pyrolytic carbon: being attached to a small amount of tar of pyrolysis carbon surface using organic solvent cleaning first, then
The residual organic solvents of pyrolysis carbon surface are cleaned using deionized water；Cleaning process carries out on supersonic wave cleaning machine, and frequency is
80kHz, scavenging period are 3h；
(4) drying and milled processed of pyrolytic carbon: filtering cleaning agent obtains clean pyrolytic carbon, pyrolytic carbon is placed in 50
DEG C baking oven in, it is dry after its moisture content be lower than 5%；Dry pyrolytic carbon is placed in grinder, be added 0.5% glycerol with
After auxiliary agent made of polyethylene wax compounding, it is fully ground 5h and obtains the pyrolytic carbon sample that partial size is 25~30 μm；Match as rubber
Filler incorporation control is 4phr when square.
Embodiment 6
(1) shell pre-processes: after cleaning the mixture that shrimp, crab shell respectively account for 50% with clear water, carrying out break process to it, obtains
To partial size 1.5~2cm shell powder sample；
(2) it is pyrolyzed shell powder sample preparation pyrolytic carbon: the shell powder sample being placed in reactor being heated by external heat source, and is led to
Cross that process control inside reactor temperature is 1000 DEG C, heat transfer medium ball temperature is about 1100 DEG C, pyrolysis time 20min；Heat
Solution starts forward reaction device and is passed through excessive inert gas so that air is discharged, and reaction stops ventilation after starting, shell broken material is heated
It is decomposed into semicoke ingredient and volatile matter, which moves together with the lifting blade in the reactor, and is conducted heat
The continuous percussion and auxiliary heat transfer of medium ball, while interacting and reacting with the volatile matter, ultimately generate target pyrolytic carbon；
(3) cleaning treatment of pyrolytic carbon: being attached to a small amount of tar of pyrolysis carbon surface using organic solvent cleaning first, then
The residual organic solvents of pyrolysis carbon surface are cleaned using deionized water；Cleaning process carries out on supersonic wave cleaning machine, and frequency is
90kHz, scavenging period are 1h；
(4) drying and milled processed of pyrolytic carbon: filtering cleaning agent obtains clean pyrolytic carbon, pyrolytic carbon is placed in 50
DEG C baking oven in, it is dry after its moisture content be lower than 5%；Dry pyrolytic carbon is placed in grinder, the 1% poly- second of oxidation is added
After auxiliary agent made of alkene wax, phthalic acid and palmitic acid compounding, it is fully ground 4h and obtains the pyrolytic carbon that partial size is 30~50 μm
Sample；Filler incorporation control is 1phr when as rubber compounding.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (9)
1. a kind of method for being pyrolyzed preparation high level gum filler based on shrimp crab based shell, which is characterized in that this method includes following
Step:
(a) pre-treatment step of shrimp and crab shells
Break process will be carried out after the cleaning of shrimp crab based shell, obtains the shell broken material that average-size is 0.5cm~2cm；
(b) preparation step of target pyrolytic carbon
Shell broken material is put into the reactor for being built-in with heat transfer medium ball, and is carried out at pyrolysis under inert gas protection
Reason, wherein inside reactor temperature is set to 300 DEG C~1000 DEG C, and pyrolysis time is set to 20min~for 24 hours；
In the process, shell broken material is heated is decomposed into semicoke ingredient and volatile matter, and the semicoke ingredient is with the reactor
Interior lifting blade moves together, and continuous percussion and auxiliary heat transfer by heat transfer medium ball, while being handed over the volatile matter
Mutual reactance ultimately generates target pyrolytic carbon；
(c) cleaning, drying and milled processed step of pyrolytic carbon
Step (b) target pyrolytic carbon generated is successively cleaned using organic solvent and deionized water, and is obtained by filtration
Clean pyrolytic carbon；This pyrolytic carbon is placed in in 50 DEG C~105 DEG C of baking oven dry certain time, makes its moisture content lower than 5%,
Then dry pyrolytic carbon is placed in grinder and is added auxiliary agent, be fully ground to obtain average grain diameter as 3 μm~50 μm most
Final product, thus to obtain required gum filler product；
Wherein the auxiliary agent is selected from one of following substance or mixture, and its additional amount accounts for the quality of the pyrolytic carbon after drying
Accounting is 3 ‰~1%: triethanolamine, diglycolamine, 2 hydroxy ethylamine, undecylene aldehyde, polyamide, glycerol, polyethylene
Wax, oxidized polyethylene wax, phthalic acid, palmitic acid.
2. the method as described in claim 1, which is characterized in that in step (b), preferably take external heat source to the reaction
Device is heated；The heat transfer medium ball is preferably sent into the reactor after external heating, and these heat transfer medium balls
It is preferably heated to 500 DEG C~1100 DEG C of temperature.
3. method according to claim 1 or 2, which is characterized in that in step (b), wrapped in target pyrolytic carbon generated
Containing the hydrophilic radicals such as the lipophilic groups such as alkyl, ester group and hydroxyl, carboxyl, promote polymer substrate interface and carbon by this method
The coupling on sour calcium surface, and the modification process of calcium carbonate can be saved.
4. method as claimed in any one of claims 1-3, which is characterized in that in step (c), it is preferred to use ultrasonic cleaning
Mode target pyrolytic carbon is cleaned, and supersonic frequency is set as 30kHz~90kHz, and scavenging period is 1h~9h.
5. the method as described in claim 1-4 any one, which is characterized in that in step (c), after being fully ground preferably
The final product for being 25 μm~30 μm to average grain diameter.
6. the method as described in claim 1-5 any one, which is characterized in that gum filler obtained preferably with 1phr~
The incorporation of 12phr prepares rubber.
7. a kind of high level gum filler product uses the method as described in claim 1-6 and prepares.
8. high level gum filler product as claimed in claim 7, which is characterized in that in above-mentioned high level gum filler product, carbon
Sour calcium grain diameter is Nano grade, and is not susceptible to agglomeration.
9. high level gum filler product as claimed in claim 7, which is characterized in that the ratio table of above-mentioned high level gum filler product
Area is 30m2/ g or more.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775816A (en) * | 2012-08-14 | 2012-11-14 | 吉林大学 | Method for preparing rubber filler by modifying coal ash waste slag obtained after extracting aluminum through acid process |
| CN103059351A (en) * | 2012-12-21 | 2013-04-24 | 暨南大学 | Biological calcium carbonate chitin, preparation method thereof and application thereof |
| CN103332970A (en) * | 2013-06-06 | 2013-10-02 | 常大勇 | Method for producing functional fertilizers by comprehensive utilization of shrimp and crab shells |
| CN104788584A (en) * | 2014-01-17 | 2015-07-22 | 厦门大学 | New technology for clean production of chitosan and carboxymethyl chitosan by using crustacean shell raw materials |
| CN105771899A (en) * | 2016-04-28 | 2016-07-20 | 农业部沼气科学研究所 | Efficient phosphorus and heavy metal removal biochar, and preparation method and application thereof |
| CN106478839A (en) * | 2015-08-28 | 2017-03-08 | 蔡敏郎 | Pretreatment method of shrimp and crab shells and method for preparing alpha-chitin |
| CN108940373A (en) * | 2018-07-16 | 2018-12-07 | 广东石油化工学院 | Based on shrimp, the organic reaction catalyst of crab waste and the preparation method and application thereof |
-
2019
- 2019-04-10 CN CN201910285297.3A patent/CN110054912B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775816A (en) * | 2012-08-14 | 2012-11-14 | 吉林大学 | Method for preparing rubber filler by modifying coal ash waste slag obtained after extracting aluminum through acid process |
| CN103059351A (en) * | 2012-12-21 | 2013-04-24 | 暨南大学 | Biological calcium carbonate chitin, preparation method thereof and application thereof |
| CN103332970A (en) * | 2013-06-06 | 2013-10-02 | 常大勇 | Method for producing functional fertilizers by comprehensive utilization of shrimp and crab shells |
| CN104788584A (en) * | 2014-01-17 | 2015-07-22 | 厦门大学 | New technology for clean production of chitosan and carboxymethyl chitosan by using crustacean shell raw materials |
| CN106478839A (en) * | 2015-08-28 | 2017-03-08 | 蔡敏郎 | Pretreatment method of shrimp and crab shells and method for preparing alpha-chitin |
| CN105771899A (en) * | 2016-04-28 | 2016-07-20 | 农业部沼气科学研究所 | Efficient phosphorus and heavy metal removal biochar, and preparation method and application thereof |
| CN108940373A (en) * | 2018-07-16 | 2018-12-07 | 广东石油化工学院 | Based on shrimp, the organic reaction catalyst of crab waste and the preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| PENGCHAO ZHANG ET AL.: "In-depth experimental study of pyrolysis characteristics of raw and cooking treated shrimp shell samples", 《RENEWABLE ENERGY》 * |
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