CN101586013B - Use of polyacrylonitrile wastes in the preparation of sealant for biogas generating pit - Google Patents
Use of polyacrylonitrile wastes in the preparation of sealant for biogas generating pit Download PDFInfo
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- CN101586013B CN101586013B CN2009100628236A CN200910062823A CN101586013B CN 101586013 B CN101586013 B CN 101586013B CN 2009100628236 A CN2009100628236 A CN 2009100628236A CN 200910062823 A CN200910062823 A CN 200910062823A CN 101586013 B CN101586013 B CN 101586013B
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- Prior art keywords
- polyacrylonitrile
- wastes
- sealant
- generating pit
- water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the use of polyacrylonitrile wastes in the preparation of a sealant for a biogas generating pit. The inventive uses the polyacrylonitrile wastes for the preparation of the sealant for the biogas generating pit and hydrolyzes polyacrylonitrile waste gel block by means of alkaline process, the generated ammonia is absorbed and utilized by water, which cause no pollution for environment; the product is good in sealing effect, simple and convenient in operation and saving in resources. The inventive sealant which is prepared by using polyacrylonitrile wastes can also be used as a seepage-proof agent for cement construction of culvert and dam.
Description
Technical field
The invention belongs to the fine chemicals industry preparation field, what be specifically related to is a kind of trade waste---the products production technology that the resource utilization of polyacrylonitrile wastes is utilized again, the air seal that particularly is applied to cement has good effect.This product also can be used as the permeability-reducing admixture of culvert, cement for dam structure body.
Background field
Polyacrylonitrile (PAN) fiber is one of three big synthon, and it can produce the waste material (comprising useless dry powder, waste silk, scrap rubber piece etc.) between 3%～5% in process of manufacture, and these waste materials can not natural degradation or hot-forming.The industrial capacity of China's acrylic fibers has nearly 1,000,000 tons.The production technique that with the Sodium Thiocyanate 99 is solvent accounts for 1/3rd.This technology, some scrap rubber that contains Sodium Thiocyanate 99 can not be used appropriately in producing the process of acrylic fibers.The scrap rubber piece that the used acrylic fibers scrap rubber piece of the present invention promptly produces under the processing condition for this reason.Utilize the polyacrylonitrile macromole to have polar-CN group, the character of products such as generation polyacrylic acid of hydrolysis under certain conditions and its esters, polyacrylamide, be to handle the most simple method of acrylic fibers scrap rubber, polyacrylonitrile hydrolyzed product is widely used in fields such as weaving slurry glue, environmental protection flocculant, oilwell water shutoff agent, agricultural high-absorbent resin, soil improvement.And polyacrylonitrile scrap rubber piece contains NaSCN, and this material environmental pollution is serious.Essential substance is a sodium polyacrylate in the hydrolyzed solution of scrap rubber piece, is called for short PAANa, and structural formula is-[CH
2-CH (COONa)-]
n-.Sodium polyacrylate is a kind of water soluble resin, and molecular weight is millions of, and colourless or light yellow viscous liquid is weakly alkaline, and energy ionization is corrosive; In the time of near pH=4, easy gel; When pH=2.5, be bordering on dissolving; Be soluble in aqueous sodium hydroxide solution, but in the aqueous solution such as calcium hydroxide, magnesium hydroxide, can precipitate; Nontoxic; Water absorbability is extremely strong.In the process that is hydrolyzed into sodium polyacrylate of scrap rubber piece, on the NaSCN that contains in the polyacrylonitrile scrap rubber piece-the CN group also is hydrolyzed, thereby the material of contaminate environment has been eliminated in the raw material.
Summary of the invention
The objective of the invention is to solve the handling problem of polyacrylonitrile wastes and the sealing problem of methane-generating pit cement, the purposes of a kind of polyacrylonitrile wastes in the preparation sealant for biogas generating pit is provided, the production process environmental friendliness, the product good sealing effect that prepare sealant for biogas generating pit with polyacrylonitrile wastes, easy and simple to handle, economize on resources.
The objective of the invention is to realize by following technical solution:
The purposes of polyacrylonitrile wastes in the preparation sealant for biogas generating pit.
Above-mentioned polyacrylonitrile wastes is for the Sodium Thiocyanate 99 being the scrap rubber piece that produces in the process of solvent production acrylic fibers.
Available bases hydrolysis method of the present invention is pressed polyacrylonitrile wastes: NaOH: H
2O=1: 0.05～0.8: 2～30 mass ratio obtains hydrolyzed solution with the polyacrylonitrile wastes hydrolysis, will use as sealant for biogas generating pit after its hydrolyzed solution and the cement mixing.
The present invention can use as sealant for biogas generating pit with cement mixing after the doping in said hydrolyzed liquid.
Added additive is a water glass; Wherein by the mass ratio hydrolyzed solution: additive: cement=100: 0.5～5.0: 20～500.
With the hydrolysis of polyacrylonitrile scrap rubber, its method is with alkali hydrolysis method: polyacrylonitrile wastes is cleaned, and be broken into the fragment that particle diameter is 1-20mm; In the mass ratio between fragment, sodium hydroxide, the water three is 1: 0.05～0.8: 2～30 ratio, fragment, sodium hydroxide and water is mixed, 90 ℃～100 ℃ reactions 2-24 hour.
The present invention prepares sealant for biogas generating pit with polyacrylonitrile wastes, adopts alkali process hydrolysis polyacrylonitrile scrap rubber piece, and the ammonia water of generation absorbs, and can not produce pollution to environment; The product good sealing effect, easy and simple to handle, economize on resources.The present invention also can be used as the permeability-reducing admixture of culvert, cement for dam structure body with the seal gum of polyacrylonitrile wastes preparation.
Embodiment
The preparation of sealant for biogas generating pit:
1. the hydrolysis of polyacrylonitrile wastes
(1) preparation of fragment
With brush will be that the polyacrylonitrile scrap rubber piece that produces in the process of solvent production acrylic fibers is cleaned with the Sodium Thiocyanate 99, and be broken into the fragment that particle diameter is 1-20mm, the blob of viscose that shears will be placed in the beaker of 1000mL, with bungee and plastic bag sealing, standby.
(2) mensuration of solid content
The mensuration of solid content: two pan papers are placed in the loft drier in 70 ℃ of dry 30min down, take out and put into moisture eliminator, be cooled to weighing after the room temperature.Take by weighing the sample of 20.98g, sample is tiled on the pan paper uniformly.Put into loft drier then, take out after 1 hour, put into the glass moisture eliminator and be cooled to weighing after the room temperature, again pan paper is put into loft drier, put into moisture eliminator behind the dry 30min and be cooled to weighing after the room temperature, repeat aforesaid operations, till the twice weighing difference in front and back is not more than 0.01g.
Solids content
X is a solids content in the formula, %; M is the pan paper quality, g; m
1Be the quality of sample before dry and pan paper, g; m
2Be sample after the drying and pan paper quality, g.
(3) hydrolysis of polyacrylonitrile wastes
All wet basis calculating in experiment with polyacrylonitrile wastes.The density of tap water is approximately 1g/mL, so replace quality to calculate with its volume in experiment.Blob of viscose is put into there-necked flask, add the NaOH particle, add tap water again, press PAN: NaOH: H between the three
2O=1: 0.05-0.8: 2-30; The reactant system of getting ready is put into the thermostatically heating magnetic stirring apparatus, reflux, temperature is raised to design temperature gradually, and temperature is set in 90 ℃～100 ℃, the ammonia that is produced in the tap water absorption reaction.
2. the hydrolyzed solution of polyacrylonitrile wastes and cement mixes
Add additive in the hydrolyzed solution with polyacrylonitrile wastes---behind the water glass directly with cement mixing after brush board, drip clear water on dried cement plate with glue head dropper, diffusion, the infiltration situation of observation water droplet are checked the water proof case of cement plate with this.
Be embodiments of the invention below.
Embodiment 1
On electronic balance, take by weighing PAN scrap rubber fragment 15.08g with cup, the scrap rubber that takes by weighing is packed in the there-necked flask; On electronic balance, take by weighing NaOH particle 6.02g with weighing bottle, load weighted NaOH particle is packed in the there-necked flask; Measure the tap water of 75mL with graduated cylinder, add in the there-necked flask; Jolting.The reactant of getting ready is put in the oil bath pan, and magneton is put into there-necked flask, reflux condensing tube is connected on bottleneck of there-necked flask intermediary again, and another mouth of reflux condensing tube clogs with soft rubber ball; Still head is connected on any one in two mouths of there-necked flask residue, and spherical condensation tube is connected on the side mouth of still head, and another mouth of still head clogs with soft rubber ball; The tail shape prolong of receiving is got an amount of tap water and is poured in the beaker of 100mL, and the water yield was not advisable just there not to be tail to take over the mouth of pipe 3～5mm.Clog the 3rd hole of there-necked flask with soft rubber ball.Plug the plug of oil bath pan, turn on the power switch, regulate the rotating speed of magneton, the temperature that oil bath pan is set is 90 ℃.In the process of reaction, the scrap rubber piece becomes orange by original beige, and is blood red, and garnet is orange red; Solution also slowly become lark, the viscosity of solution is also changed from small to big, along with the prolongation of hydrolysis time, viscosity diminishes again.Treat that it is the hydrolysis reaction terminal point that blob of viscose disappears.Reaction times is 5 hours.
On electronic balance, take by weighing PAN hydrolyzed solution 20.05g (it is heavy not contain cup) with cup, add cement 19.19g with the decrement method and (adorn big half cup cement with cup, be placed on weighing on the electronic balance, record data, get cement with spoon in cup and put into the cup that claims to have the PAN hydrolyzed solution, stir with glass stick, the limit edged stirs, be linear up to mud and flow down, the registration on record balance this moment; Two data subtract each other promptly get add the consumption of cement), stir, with brush with clay bruss on plank, approximately after half an hour or see that the lip-deep water of mud on the plank disappears, and brushes second time again; Etc. brushing again after about half an hour the 3rd time.After treating that brush board has been done, drip clear water onboard, water droplet indiffusion in 27 minutes with glue head dropper.
Embodiment 2
On electronic balance, take by weighing PAN scrap rubber fragment 15.01g with cup, the scrap rubber that takes by weighing is packed in the there-necked flask; On electronic balance, take by weighing NaOH particle 4.49g with weighing bottle, load weighted NaOH particle is packed in the there-necked flask; Measure the tap water of 75mL with graduated cylinder, add in the there-necked flask; Jolting.The reactant of getting ready is put into oil bath pan, again magneton is put into there-necked flask; Reflux condensing tube is connected on bottleneck of there-necked flask intermediary, and another mouth of reflux condensing tube clogs with soft rubber ball; Still head is connected on any one in two mouths of there-necked flask residue, and spherical condensation tube is connected on the side mouth of still head, and another mouth of still head clogs with soft rubber ball; The tail shape prolong of receiving is got a certain amount of tap water and is poured in the beaker of 100mL, and the water yield was not advisable just there not to be tail to take over the mouth of pipe 3～5mm.Clog the 3rd hole of there-necked flask with soft rubber ball.Plug the plug of oil bath pan, turn on the power switch, regulate the rotating speed of magneton, the temperature that oil bath pan is set is 90 ℃.Reaction times is 5.5 hours, gets hydrolyzed solution.
On electronic balance, take by weighing PAN hydrolyzed solution 7.97g (it is heavy not contain cup) with cup; Add the 0.08g water glass in hydrolyzed solution, stirring obtains PAN hydrolyzed solution mixture.Measuring the 5mL tap water with graduated cylinder adds in the cup that the PAN hydrolyzed solution is housed; Add cement 24.85g with the decrement method; Stir brush board.After treating that brush board has been done, drip clear water onboard, water droplet indiffusion in 30 minutes with glue head dropper.
Embodiment 3
On electronic balance, take by weighing PAN hydrolyzed solution 20.57g (it is heavy not contain cup) with cup; Add the 0.26g water glass in hydrolyzed solution, stirring obtains PAN hydrolyzed solution mixture.Add cement 60.65g with the decrement method; Stir brush board.After treating that brush board has been done, drip clear water onboard, water droplet indiffusion in 35 minutes with glue head dropper.
Take by weighing the sealing agent of the commercially available polyvinyl alcohol of 20g, add the 120mL hot water dissolving after, add the cement mixing of 400g, stir brush board.After treating that brush board has been done, drip several clear water onboard, water droplet indiffusion in 18 minutes with glue head dropper.
The PAN hydrolyzed solution is as the cement seal agent, with brush board after the cement mixing, and after plate is done, outward appearance and better than the sealing agent that uses commercially available polyvinyl alcohol, and also the surface is more smooth, also has a skim.Cohesiveness is the same, and setting rate is slow slightly.
Embodiment 4
On table scale with taking by weighing PAN hydrolyzed solution 100kg; Add the 1kg water glass in hydrolyzed solution, stirring obtains PAN hydrolyzed solution mixture.Add cement 300kg with the decrement method; Stir brush board.After treating that brush board has been done, drip several clear water onboard, water droplet indiffusion in 32 minutes with glue head dropper.
Take by weighing the sealing agent of the commercially available polyvinyl alcohol of 100kg, add the 600L hot water dissolving after, add the cement mixing of 2000kg, stir brush board.After treating that brush board has been done, drip several clear water onboard, water droplet indiffusion in 20 minutes with glue head dropper.
The PAN hydrolyzed solution is as the cement seal agent, with brush board after the cement mixing, and after plate is done, outward appearance and better than the sealing agent that uses commercially available polyvinyl alcohol, and also the surface is more smooth, also has a skim.Cohesiveness is the same, and setting rate is slow slightly.
Claims (5)
1. polyacrylonitrile wastes is in the purposes of preparation in the sealant for biogas generating pit; Press polyacrylonitrile wastes with alkali hydrolysis method: NaOH: H
2O=1: 0.05～0.8: 2～30 mass ratio obtains hydrolyzed solution with the polyacrylonitrile wastes hydrolysis, will use as sealant for biogas generating pit after its hydrolyzed solution and the cement mixing.
2. purposes according to claim 1 is characterized in that: described polyacrylonitrile wastes is for the Sodium Thiocyanate 99 being the scrap rubber piece that produces in the process of solvent production acrylic fibers.
3. purposes according to claim 1 is characterized in that: use as sealant for biogas generating pit with cement mixing after the doping in hydrolyzed solution.
4. purposes according to claim 3 is characterized in that: added additive is a water glass; Wherein by the mass ratio hydrolyzed solution: additive: cement=100: 0.5～5.0: 20～500.
5. according to claim 3 or 4 described purposes, it is characterized in that: with the hydrolysis of polyacrylonitrile scrap rubber, its method is with alkali hydrolysis method: polyacrylonitrile wastes is cleaned, and be broken into the fragment that particle diameter is 1-20mm; In the mass ratio between fragment, sodium hydroxide, the water three is 1: 0.05～0.8: 2～30 ratio, fragment, sodium hydroxide and water is mixed, 90 ℃～100 ℃ reactions 2-24 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100628236A CN101586013B (en) | 2009-06-23 | 2009-06-23 | Use of polyacrylonitrile wastes in the preparation of sealant for biogas generating pit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100628236A CN101586013B (en) | 2009-06-23 | 2009-06-23 | Use of polyacrylonitrile wastes in the preparation of sealant for biogas generating pit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101586013A CN101586013A (en) | 2009-11-25 |
| CN101586013B true CN101586013B (en) | 2011-11-30 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2009100628236A Expired - Fee Related CN101586013B (en) | 2009-06-23 | 2009-06-23 | Use of polyacrylonitrile wastes in the preparation of sealant for biogas generating pit |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103215181B (en) * | 2013-04-17 | 2014-07-23 | 山东省农业科学院蔬菜研究所 | Internal and external sealing treatment method for biogas digester |
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- 2009-06-23 CN CN2009100628236A patent/CN101586013B/en not_active Expired - Fee Related
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| CN101586013A (en) | 2009-11-25 |
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