CN102010683A - Method for controlling lignin-phenolic resin adhesive reaction end point - Google Patents
Method for controlling lignin-phenolic resin adhesive reaction end point Download PDFInfo
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- CN102010683A CN102010683A CN2010105240200A CN201010524020A CN102010683A CN 102010683 A CN102010683 A CN 102010683A CN 2010105240200 A CN2010105240200 A CN 2010105240200A CN 201010524020 A CN201010524020 A CN 201010524020A CN 102010683 A CN102010683 A CN 102010683A
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- Prior art keywords
- acid
- lignin
- resin adhesive
- phenolic resin
- brown
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000000853 adhesive Substances 0.000 title claims abstract description 18
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 18
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 14
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 13
- 238000001514 detection method Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000005070 sampling Methods 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 18
- 238000003756 stirring Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229920005610 lignin Polymers 0.000 abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000020477 pH reduction Effects 0.000 abstract 2
- 241001391944 Commicarpus scandens Species 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 229920003987 resole Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 4
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000003351 stiffener Substances 0.000 description 2
- LMODBTYAMBSWQE-UHFFFAOYSA-N (2-hydroxyphenyl)methanetriol Chemical compound OC1=CC=CC=C1C(O)(O)O LMODBTYAMBSWQE-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to a method for controlling a lignin-phenolic resin adhesive reaction end point. The method comprises the following steps of: sampling and performing acidification and detection, wherein the acidification is to add 2 to 5mol/L acid solution into the taken sample in a stirring state until cakes are generated; the detection is to detect the cakes; and when the cakes are brown, can be lengthened by stretching after being taken out but are easy to break, and a fracture surface has brown gloss, the end point is achieved. The control method is not limited by the proportion that phenol is substituted by the lignin, is not influenced by the polymerization reaction process of the lignin, the phenol and formaldehyde, and simply, fast, conveniently, visually, accurately and reliably reflects the end point of the lignin-phenolic resin adhesive reaction, so that a reliable, economical and convenient detection method is provided for the industrialized production of a lignin-based phenolic resin adhesive.
Description
One, technical field
The present invention relates to a kind of control method of chemical reaction terminal point, specifically a kind of control method of alkali lignin-phenolic resin compounded sizing agent reaction end.
Two, background technology
Traditional synvaren is formed through polyreaction by phenol and formaldehyde under alkaline condition, and its bonding strength is decided by the size of its intermolecular extent of polymerization and molecular weight thereof; When polymerization was not enough, the molecular weight of resin was little, and bonding strength is just little, and when polymerization was excessive, the molecular weight of resin was excessive, and bonding strength also reduces.Therefore, in actual production, in time grasping the extent of polymerization of resin, stop its polyreaction, make the bonding strength of resin reach best, is the key of decision synvaren collagen amount.Traditional detection resol extent of polymerization method has viscosity measurements method, molecular weight detection method, atomizing observation etc. several, and concrete operations are as follows:
(1) viscosity measurements method: be the National Standard Method that detects the Phenol aldehyde resin extent of polymerization, promptly in the preparation process of Phenol aldehyde resin, adopt rotational viscosimeter or be coated with the viscosity that the Resin adhesive of polyreaction is being carried out in four glasss of continuous detections, when its viscosity reaches certain numerical value, cooling immediately, stop its polyreaction, can obtain the product tackiness agent.
(2) molecular weight detection method: in the preparation process of Phenol aldehyde resin, along with constantly polymerization between molecular resin, its molecular weight increases gradually, detect by continuous sampling, when its polymerization acquires a certain degree, cool off immediately when the molecular weight size reaches requirement, stop its polyreaction, promptly obtain the product tackiness agent.
(3) atomizing observation: this is enterprise's easy detection method commonly used.In the preparation process of Phenol aldehyde resin, will just constantly take a sample at polymeric glue, be added drop-wise in the clear water; At the polymerization initial stage, the molecular weight of Resin adhesive is little, is uniformly dispersed in water and transparent, atomizating phenomenon can not occur; When Resin adhesive was aggregated to a certain degree, its molecular weight was enough big, can not dissolve in water, milky atomizating phenomenon will occur.When the oyster white atomizing occurs, add water cooling immediately, stop its polyreaction, emit when being reduced to 40-50 ℃ and obtain the product tackiness agent.
In order to reduce the dependence to petroleum resources, the applicant adopts xylogen to substitute part phenol and produces xylogen--and synvaren has also been applied for Chinese invention patent (201010269425.4).But when this sizing agent of preparation, the applicant adopts traditional viscosity measurements method control reaction end.But practice shows that the measured viscosity numerical value of viscosity apparatus often can not correctly reflect the terminal point of reaction, influences quality product; The molecular weight detection method, the apparatus expensive complex operation, the production of incompatibility tracking monitor needs.Though the atomizing observation is simple, because xylogen liquid is black, influence range estimation effect, same sample often varies with each individual, and obtains different results.
Three, summary of the invention
The present invention is directed in the alkali lignin-phenolic resin compounded sizing agent preparation process reaction end and control existing problem, the control method that aims to provide a kind of new reaction end is with preparation quality is stable, cohesive strength is high sizing agent, technical problem to be solved is that end-point control method has versatility, promptly be not subjected to the influence of factors such as lignin molecule amount size, reaction solution concentration, pH value, material rate, can reflect the reaction end of each still material correctly, objectively.
The alleged reaction end of the present invention is meant that extent of polymerization reaches the terminal point that best one-tenth glue needs.The cohesive strength of compound sizing agent is the highest under this terminal point.
Xylogen-phenolic resin adhesive is the resol that reaction forms under the basic catalyst effect.The pH value of reaction medium is greater than 7 under the basic catalyst effect, addition reaction at first takes place and generates a methylolphenol in phenol, xylogen and formaldehyde, under the room temperature, phenolic alcohol in the alkaline medium is stable, therefore a methylolphenol is not easy further polycondensation, can only generate hydroxymethyl-phenol and tri hydroxy methyl phenol.Further condensation after the methylolphenol of above generation is heated forms resole.The resol that this class contains methylol is hot admittedly.
Acid also is the stiffening agent of resol.Acid hardening is similar to the mechanism of heat embrittlement, adds acid in the liquid state resole, when pH less than 2 the time, just can harden under the normal temperature.The acids stiffening agent can be suitable mineral acid or organic acid, and commonly used have hydrochloric acid or phosphoric acid, and tosic acid, sulfocarbolic acid or other sulfonic acid are also arranged.
The applicant has carried out deep research to this polyreaction, thinks can be divided into three phases from beginning to be polymerized to reaction end:
At the initial stage of polyreaction, the extent of polymerization between molecular resin is not high, and the molecular resin amount is big inadequately, and the throw out that the heavy back of acid forms is brown, and snappiness is strong, can stretch to extend into the filament shape, is referred to as the A stage.
Along with further carrying out of polyreaction between molecular resin, the intermolecular polymerization degree increases, the molecule quantitative change is big, the brown throw out snappiness that adds the formation of acid back reduces gradually, fragility increases gradually, the silk of pulling out brokenly slowly becomes easily disconnected brokenly by not easily broken, and presents the shinny section of brown, is referred to as the B stage.This moment, the extent of polymerization of Resin adhesive reached best, and bonding strength reaches maximum value.Described terminal point control is exactly that controlled polymerization stops during the stage at B.
Further continuity along with polyreaction between molecular resin, molecular weight continues to increase, the throw out that adds after the acid becomes the gray fine particle of mud by the brown bulk, no longer have snappiness, can not pull into threadly, be referred to as the C stage, in this stage, though the extent of polymerization of Resin adhesive further increases, its bonding strength no longer increases, and reduces gradually on the contrary.
The control method of this xylogen-phenolic resin adhesive reaction end comprises sampling, acidifying and detection, described sampling is after xylogen-the phenolic resin adhesive preparation enters polymerization stage 10-15 minute, begin the 10-50mL that takes a sample, detect once every the 5-10min sampling then; Described acidifying adds concentration 2-5mol/L acid solution exactly while stirring in sample, be block gradually until sample; Described detection detects block exactly, and in the polymerization A stage, the acid that adds the acid stirring separates out the softening bar that thing presents brown, and stretching can be extended into filament; The polymerization B stage, prolongation along with polymerization time, extent of polymerization increases, and adds the ductility that acid that acid stirs separates out thing and reduces gradually, and fragility increases gradually, when but the brown bulk can also be elongated very easily broken broken, when section presented the shinny gloss of brown, the extent of polymerization of composite adhesive molecule reached best one-tenth glue needs, and lower the temperature this moment immediately, stop intermolecular polyreaction, can obtain the highest product tackiness agent of bonding strength when being cooled to 40 ℃-45 ℃.The polymerization C stage: if when the acid out throw out becomes the gray fine particle of mud by the brown massive transformation in whipping process, show that promptly the extent of polymerization of xylogen-phenolic resin adhesive molecule has surpassed the one-tenth glue needs (being commonly called as glue has done always) of tackiness agent, the tackiness agent that this moment, cooling obtained, its bonding strength reduce greatly.
Described acid solution is selected from acid solutions such as hydrochloric acid, phosphoric acid, tosic acid, sulfocarbolic acid or other sulfonic acid.
Whether the polyreaction that the present invention can understand in xylogen-phenolic resin adhesive preparation process in time, intuitively and accurately is in the B stage, so that cooling in time, stop polyreaction, obtain the lignin phenol formaldehyde resin composite adhesive product of extent of polymerization the best, bonding strength maximum.
The present invention compares with traditional synvaren detection method (viscosity measurements method, molecular weight detection method, atomizing detection method), has following advantage:
This detection method does not need Special Equipment, be not subjected to the color of xylogen liquid, lignin molecule amount size, condition effect such as the concentration of reaction liquid, not being subjected to xylogen to substitute the phenol ratio limits, be not subjected to xylogen yet, phenol, the influence of oxymethylene polymerization reaction mechanism, simple and fast, convenient, intuitively, accurately, reflecting xylogen reliably--the resol intermolecular polymerization reacts the residing stage, understand its polymeric degree, and then obtain the tackiness agent of best bonding strength, avoided the error that subjective judgement produced, for the suitability for industrialized production of lignin-base phenolic resin adhesive provides reliable, economy is detection method easily.
Four, embodiment
Below by case study on implementation the present invention is further described.
Embodiment 1:
To contain 22% admittedly, the high-activity alkali xylogen liquid 365kg of pH13.5 and 120kg phenol (xylogen substitutes 40% phenol), formaldehyde 220kg (total amount 80%) adds reactor, behind thorough mixing under the 40-60 ℃ of condition, add 30% liquid caustic soda 55kg (total amount 80%), be warmed up to 85-100 ℃ in the 30min, behind the insulation reaction 30min, the water that adds remaining liquid caustic soda and total rubber 20%, behind the 80-85 ℃ of insulation 10min, add remaining formaldehyde and stir, after being warmed up to 85-100 ℃ of insulation 10min, carry out following detection: pour small beaker into from reactor sampling 20ml with graduated cylinder, slowly add 4mol/L hydrochloric acid, the limit adds sour limit and stirs up to throw out occurring, observe sedimentary color and detect toughness, detect once every 10min, when brown throw out snappiness reduces gradually, it is disconnected broken easily that fragility is increased to the silk of pulling out gradually, when section has brown gloss, cooling at once, stop polyreaction, plastic emitting when being cooled to 40-45 ℃, the bonding strength of this composite caking agent is high, and the bamboo offset plate of production reaches national category-A plate standard (according to the standard of LY/T1574-2000).
Embodiment 2:
To contain 20% admittedly, the high-activity alkali xylogen liquid 365kg of pH13.5 and 80kg phenol (xylogen substitutes 50% phenol), formaldehyde 204kg (total amount 80%) adds reactor, behind thorough mixing under the 40-60 ℃ of condition, add 30% liquid caustic soda 52kg (total amount 80%), be warmed up to 85-100 ℃ in the 30min, behind the insulation reaction 30min, the water that adds remaining liquid caustic soda and total rubber 20%, behind the 80-85 ℃ of insulation 10min, add remaining formaldehyde and stir, after being warmed up to 85-100 ℃ of insulation 10min, carry out following detection: pour small beaker into from reactor sampling 20ml with graduated cylinder, slowly add 2mol/L phosphoric acid, the limit adds sour limit and stirs until throw out occurring, observe sedimentary color and detect toughness, detect once every 10min, when brown throw out snappiness reduces gradually, it is disconnected broken easily that fragility is increased to the silk of pulling out gradually, when section has brown gloss, cooling at once, stop polyreaction, plastic emitting when being cooled to 40-45 ℃, the bonding strength of this composite caking agent is high, and the bamboo offset plate of production reaches national category-A plate standard (according to the standard of LY/T1574-2000).
Embodiment 3:
With contain 20% admittedly, high-activity alkali xylogen liquid 300kg and 140kg phenol (xylogen substitutes 30% phenol), the formaldehyde 260kg of pH13.5 add reactor, behind thorough mixing under the 40-60 ℃ of condition, the liquid caustic soda 60kg of adding 30%, be warmed up to 85-100 ℃ in the 30min, behind the insulation reaction 40min, carry out following detection: pour small beaker with graduated cylinder into from reactor sampling 20ml, slowly add the 5mol/L tosic acid, the limit adds sour limit and stirs until throw out occurring.Observe sedimentary color and detect toughness, detect once every 10min, when brown throw out snappiness reduces gradually, it is disconnected broken easily that fragility is increased to the silk of pulling out gradually, when section has brown gloss, and cooling at once, stop polyreaction, plastic emitting when being cooled to 40-45 ℃, the bonding strength of this composite caking agent is high, and the bamboo offset plate of production reaches national category-A plate standard (according to the standard of LY/T1574-2000).
Claims (2)
1. the control method of xylogen-phenolic resin adhesive reaction end, comprise sampling, acidifying and detection, it is characterized in that: described acidifying is exactly under agitation to add concentration 2-5mol/L acid solution until being block in the sample of being got, described detection detects block exactly, can extend into filament when block is brown and take out stretches, the expression terminal point does not arrive, when the stretching variable length but easily brittle failure, and section has brown gloss, and the expression terminal point arrives.
2. control method according to claim 1 is characterized in that: described acid solution is selected from the acid solution of hydrochloric acid, phosphoric acid, tosic acid, sulfocarbolic acid or other sulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010524020 CN102010683B (en) | 2010-10-27 | 2010-10-27 | Method for controlling lignin-phenolic resin adhesive reaction end point |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010524020 CN102010683B (en) | 2010-10-27 | 2010-10-27 | Method for controlling lignin-phenolic resin adhesive reaction end point |
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| Publication Number | Publication Date |
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| CN102010683A true CN102010683A (en) | 2011-04-13 |
| CN102010683B CN102010683B (en) | 2012-12-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977298A (en) * | 2012-11-27 | 2013-03-20 | 山东圣泉化工股份有限公司 | Lignin and boronic acid modified phenolic resin and method for preparing same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1570008A (en) * | 2003-07-23 | 2005-01-26 | 中国科学院上海原子核研究所 | Production method of phenol aldehyde resin adhesive for timber and ferula |
| CN1632030A (en) * | 2004-08-03 | 2005-06-29 | 曲韵丰 | Composite phenolic resin glue producing method |
-
2010
- 2010-10-27 CN CN 201010524020 patent/CN102010683B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1570008A (en) * | 2003-07-23 | 2005-01-26 | 中国科学院上海原子核研究所 | Production method of phenol aldehyde resin adhesive for timber and ferula |
| CN1632030A (en) * | 2004-08-03 | 2005-06-29 | 曲韵丰 | Composite phenolic resin glue producing method |
Non-Patent Citations (2)
| Title |
|---|
| 庞小仁: "脲醛树脂生产中的反应终点控制", 《木材工业》, vol. 5, no. 4, 30 November 1991 (1991-11-30), pages 54 * |
| 栗明英: "脲醛树脂反应终点的控制", 《粘接》, vol. 25, no. 2, 10 April 2004 (2004-04-10), pages 47 - 48 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977298A (en) * | 2012-11-27 | 2013-03-20 | 山东圣泉化工股份有限公司 | Lignin and boronic acid modified phenolic resin and method for preparing same |
| CN102977298B (en) * | 2012-11-27 | 2014-06-25 | 山东圣泉化工股份有限公司 | Lignin and boronic acid modified phenolic resin and method for preparing same |
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| Publication number | Publication date |
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| CN102010683B (en) | 2012-12-19 |
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Effective date of registration: 20160414 Address after: 232200, Lu'an, Anhui province Shouxian County Liu Liu town, west of harvest road, north side of pioneering Road Patentee after: Lattice justice circular economy industrial garden, Anhui company limited Address before: 237200 Anhui Economic Development Zone, Mount Holyoke, three Patentee before: Anhui Geyi Cleaning Energy Technology Co., Ltd. |
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Address after: 232200 Anhui, Lu'an, Shouxian County, Yan Liu town, harvest Avenue, the west side of pioneering Avenue North Patentee after: China CITIC recycling economy Co., Ltd. Address before: 232200 Anhui, Lu'an, Shouxian County, Yan Liu town, harvest Avenue, the west side of pioneering Avenue North Patentee before: Lattice justice circular economy industrial garden, Anhui company limited |