CN105032903A - Method for removing chloride ions in waste alkaline residues - Google Patents
Method for removing chloride ions in waste alkaline residues Download PDFInfo
- Publication number
- CN105032903A CN105032903A CN201510563512.3A CN201510563512A CN105032903A CN 105032903 A CN105032903 A CN 105032903A CN 201510563512 A CN201510563512 A CN 201510563512A CN 105032903 A CN105032903 A CN 105032903A
- Authority
- CN
- China
- Prior art keywords
- waste soda
- soda residue
- waste
- residue
- dechlorination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a method for removing chloride ions in waste alkaline residues. The method specifically includes the steps that the waste alkaline residues and magnetic substances are evenly mixed according to the mass ratio of 100:0.1-1.5; water with the mass three to six times that of the waste alkaline residues is added; the mixture is fully stirred, water elution, dechlorination and solid-liquid separation are conducted, and then deposits and supernate are obtained; the deposits are dried; and the magnetic substances are removed through a magnet, and then dechlorinated alkaline residues with 90-93% of chloride removed is obtained. The method has the beneficial effects that the settling velocity of the alkaline residues is high, the alkaline residue dechlorination efficiency is high, and the water content of the dechlorinated alkaline residues is low. Meanwhile, the process and equipment are simple, operation is easy, and energy consumption is low. By means of the method, the waste alkaline residues in soda production by the ammonia-soda process are applied to broader fields in a large scale.
Description
Technical field
The invention belongs to ammonia-soda process soda manufacture dreg liquid field of comprehensive utilization, particularly a kind of method removing chlorion in waste soda residue.
Background technology
There is the method for three productions soda ash at present in the world, i.e. ammonia-soda process, union soda and natural alkaline process.Large enterprise is in the majority with ammonia-soda process, accounts for production about more than 60%.But ammonia-soda process is come out over more than 130 year, because production technology reason produces a large amount of alkaline waste liquor and waste residue, often produce 1t soda ash, need the solid alkaline residue discharging 1t water content about 30 ~ 60%, because high, the chloride height of its pH value, hygroscopicity are strong, international and domestic also not effective a large amount of disposal options at present, most enterprise Yi Dui saves as master, the alkaline residue that whole nation accumulation has been stored up, more than 100,000,000 tons, constrains the sustainable development of ammonia-soda process enterprise, has become a great problem of world's soda industry development.
The main component of alkaline residue is CaCO
3, Mg(OH)
2, MgCl
2, CaCl
2, NaCl etc., wherein chlorinty is about 8-15%, utilize to some extent in fields such as engineering construction, chemical industry, environmental protection, agriculture fishery at present, but due to chloride height, feature that hygroscopicity is large, various reuse method is restricted, as as during the construction material such as brickmaking or cement due in alkaline residue containing comparatively high chloride ion, the hydrogen chloride of perishable pipeline and equipment is produced under higher temperature conditions, also harmful effect is had to the intensity of product and mechanical performance, brick and motar, because affecting by chloride, produce scum phenomenon after a procedure and its use value are reduced; Because muriatic loss by dissolution causes qualitative problems of construction when backfilling for pavement construction and tunnel; Also hydrogen-chloride etching problem is there is as when shaped coal additive, steam coal burning desulfurizing agent and fume desulfurizing agent; As causing soil compaction when soil conditioner, the application of calcium magnesium Chemical Mixed Fertilizer because chlorinty is high and suppressing the problems such as plant growth, the chlorion therefore effectively removed in alkaline residue has become significant bottleneck problem and the key technology of waste soda residue discharge and comprehensive utilization.
Extensive research is carried out to waste soda residue dechlorination both at home and abroad, mainly contained washing method, ion-exchange-resin process and electrolysis.Washing method mainly adopts fresh water or seawater to be carrying out washing treatment agent, as Chinese patent CN1098817C adopts municipal sewage to process agent removing waste soda residue chlorion, waste soda residue and municipal sewage weight ratio are 20 ~ 80: 1000, dechlorination effect reaches more than 93%, but water consumption is large, and the problem that when there is, washing tiny by the granularity because of waste soda residue, sinking speed causes the dechlorination time long slowly, wash storage, transport and use that rear waste soda residue water-retaining property affects by force next step, produce chlorion secondary pollution problem simultaneously.Ion-exchange-resin process and electrolysis are because of needs particular filter resin material, and cost is high and easily block, and are only in the exploratory stage at present.
The present invention utilizes Magneto separate water-washing technique, by changing alkaline residue particle surface chemical property, utilizing 3-6 doubly alkaline residue dechlorination efficiency just can be made to reach more than 90% to the water yield of alkaline residue, providing new method for alkaline residue becomes available regenerated resources.
Summary of the invention
The invention provides a kind of method removing chlorion in waste soda residue, to solve current waste soda residue cannot to realize large-scale comprehensive recycling problem because chloride ion content is large.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind of method removing chlorion in waste soda residue, waste soda residue is mixed according to mass ratio 100:0.1 ~ 1.5 with magnetisable material, adds the water of waste soda residue quality 3 ~ 6 times, fully stir, carry out washing dechlorination, then Separation of Solid and Liquid, is precipitated thing and supernatant, described drying precipitate, remove magnetisable material with magnet, obtain dechlorination alkaline residue.
Magnetisable material of the present invention is any one or a few in magnetic powder, magnetite powder or ground hematite.
Magnetisable material granularity of the present invention is 2 ~ 10 μm.
Waste soda residue of the present invention and magnetisable material mass ratio 100:0.5 ~ 1.
When waste soda residue of the present invention carries out washing dechlorination, adopt the magnetostatic field of additional 4000 ~ 6000Gauss.
Washing dechlorination mixing time of the present invention is 0.5 ~ 1h.
Solid-liquid separating method of the present invention is standing separation method or leaves standstill-centrifugal process.
Drying means of the present invention is natural drying method, and the time is 4 ~ 5d.
Waste soda residue of the present invention, before washing dechlorination, carries out pretreatment, makes waste soda residue more than 90% granularity≤1mm.
Preprocess method of the present invention is cal rolling method.
Waste soda residue of the present invention is the waste soda residue that ammonia-soda process soda ash produces.
Mentality of designing of the present invention is: the present invention's key character utilizes magnetic separation technique to realize the Fast Stripping of chlorion in water, makes dechlorination alkaline residue chlorinty <2%, moisture content <10%.As everyone knows, waste soda residue is made up of non-dissolved salt and soluble salt, and the main component of non-dissolved salt is the bad secondary CaCO of granular crystal
3and CaSO
4, account for more than 80 ~ 90% of waste soda residue, soluble salt is mainly chlorine-containing compound as CaCl
2, NaCl, MgCl
2deng, wherein Cl
-account for 10 ~ 15% of waste soda residue total amount.Due to soluble salt in waste soda residue and the tiny mixed crystal of non-dissolved salt Crystallization or solid solution, and hole is flourishing, when therefore directly utilizing water to mix with waste soda residue, the stripping in water of chloride lyotropic salt is slower, stripping quantity is lower, obtains high needing large water gaging except chlorine dose and repeatedly wash if want.After waste soda residue mixes with water by the present invention under externally-applied magnetic field and stirring action, hydrone is owing to being subject to the effect rearrangement of Lorentz force, hydrone dipole moment deflects, reduce the hydrogen bond between hydrone, the catenulate water cluster that makes originally to associate fragments into single Small molecular, easily make the zwitterions such as Ca, Na, Mg, Cl be surrounded by single hydrone and form stable hydrated ion, thus accelerate the ionization of lyotropic salt, make Cl
-in water, solubility increases, and stripping quantity increases; Simultaneously molecular dynamics simulation proves that Ca, Na, Mg plasma diffusion coefficient in magnetic field increases, make its easily from the hole of alkaline residue solid expanding effusion enter in water, make Cl
-in water, dissolution velocity increases and solubility increase.Therefore experiment proves only can reach with 3-6 times of water agitator treating certain hour the object that rapid, high volume removes chlorion in waste soda residue in magnetic field.
The beneficial effect adopting technique scheme to produce is: 1, use magnetic separation technique to remove the chlorion in ammonia-soda process soda manufacture waste soda residue at home and abroad first, take water as dechlorination inorganic agent, externally-applied magnetic field during dechlorination, water consumption is only the 3-6 of alkaline residue doubly, and alkaline residue dechlorination efficiency reaches more than 90%; 2, gained dechlorination alkaline residue is easily dry, adopt natural drying that moisture content can be made to be reduced to less than 10%, break through the adverse effect of chlorion during alkaline residue comprehensive utilization, provide technical foundation for alkaline residue utilizes on a large scale in fields such as building, road traffic, agricultural, environment, chemical industry, metallurgy; 3, the invention provides the method removing chlorion in ammonia-soda process soda manufacture waste soda residue fast, take water as dechlorination inorganic agent, externally-applied magnetic field during process, there is alkaline residue sinking speed fast, the feature that alkaline residue dechlorination efficiency is high, dechlorination alkaline residue moisture content is low, technology and equipment is simple simultaneously, easily operates, the less energy consumption consumed, the application that the extensive utilization that the present invention is ammonia-soda process soda manufacture waste soda residue provides scope wider.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further detailed explanation; Each embodiment alkaline residue dechlorination effect is in table 1.
Embodiment 1
Waste soda residue is carried out cal rolling pretreatment, makes waste soda residue more than 90% granularity≤1mm.Waste soda residue is mixed according to mass ratio 100:1 with magnetic powder, the magnetostatic field of additional 4000Gauss, add the water of waste soda residue quality 4 times, fully stir 0.5h, carry out washing dechlorination, then standing separation, be precipitated thing and supernatant, the described sediment right dryness in the sun time is 4d, to water content <10%, remove magnetic powder with magnet, obtain dechlorination alkaline residue.
Embodiment 2
Waste soda residue is carried out cal rolling pretreatment, makes waste soda residue more than 90% granularity≤1mm.Waste soda residue is mixed according to mass ratio 100:1.2 with magnetic powder, the magnetostatic field of additional 5000Gauss, add the water of waste soda residue quality 5 times, fully stir 0.5h, carry out washing dechlorination, then standing separation, be precipitated thing and supernatant, the described sediment right dryness in the sun time is 5d, to water content <10%, remove magnetic powder with magnet, obtain dechlorination alkaline residue.
Embodiment 3
Waste soda residue is carried out cal rolling pretreatment, makes waste soda residue more than 90% granularity≤1mm.Waste soda residue is mixed according to mass ratio 100:1.2 with magnetic iron ore, the magnetostatic field of additional 4000Gauss, add the water of waste soda residue quality 4 times, fully stir 0.5h, carry out washing dechlorination, then standing separation, be precipitated thing and supernatant, the described sediment right dryness in the sun time is 4d, to water content <10%, remove magnetic iron ore with magnet, obtain dechlorination alkaline residue.
Embodiment 4
Waste soda residue is carried out cal rolling pretreatment, makes waste soda residue more than 90% granularity≤1mm.Waste soda residue is mixed according to mass ratio 100:1.4 with magnetic iron ore, the magnetostatic field of additional 5000Gauss, adds the water of waste soda residue quality 5 times, fully stirs 1h, carry out washing dechlorination, then leave standstill 1.5h, centrifugation, is precipitated thing and supernatant, the described sediment right dryness in the sun time is 4d, to water content <10%, remove magnetic iron ore with magnet, obtain dechlorination alkaline residue.
Embodiment 5
Waste soda residue is carried out cal rolling pretreatment, makes waste soda residue more than 90% granularity≤1mm.Waste soda residue is mixed according to mass ratio 100:0.5 with magnetic powder, the magnetostatic field of additional 4000Gauss, add the water of waste soda residue quality 6 times, fully stir 1h, carry out washing dechlorination, then standing separation, be precipitated thing and supernatant, the described sediment right dryness in the sun time is 5d, to water content <10%, remove magnetic powder with magnet, obtain dechlorination alkaline residue.
Embodiment 6
Waste soda residue is carried out cal rolling pretreatment, makes waste soda residue more than 90% granularity≤1mm.Waste soda residue is mixed according to mass ratio 100:1.5 with magnetite powder and ground hematite mixture (waiting mass ratio), the magnetostatic field of additional 4000Gauss, adds the water of waste soda residue quality 5 times, fully stirs 1h, carry out washing dechlorination, then leave standstill 1h, centrifugation, is precipitated thing and supernatant, the described sediment right dryness in the sun time is 4d, to water content <10%, remove magnetite powder, ground hematite mixture with magnet, obtain dechlorination alkaline residue.
Embodiment 7
Waste soda residue is carried out cal rolling pretreatment, makes waste soda residue more than 90% granularity≤1mm.Waste soda residue is mixed according to mass ratio 100:0.1 with magnetic powder, the magnetostatic field of additional 6000Gauss, add the water of waste soda residue quality 3 times, fully stir 0.5h, carry out washing dechlorination, then standing separation, be precipitated thing and supernatant, the described sediment right dryness in the sun time is 5d, to water content <10%, remove magnetic powder with magnet, obtain dechlorination alkaline residue.
Table 1 alkaline residue dechlorination effect
The invention provides the method removing chlorion in ammonia-soda process soda manufacture waste soda residue fast, take water as dechlorination inorganic agent, externally-applied magnetic field during process, there is alkaline residue sinking speed fast, the feature that alkaline residue dechlorination efficiency is high, dechlorination alkaline residue moisture content is low, technology and equipment is simple simultaneously, easily operates, the less energy consumption consumed, the application that the extensive utilization that the present invention is ammonia-soda process soda manufacture waste soda residue provides scope wider.
Claims (10)
1. remove the method for chlorion in waste soda residue for one kind, it is characterized in that, waste soda residue is mixed according to mass ratio 100:0.1 ~ 1.5 with magnetisable material, adds the water of waste soda residue quality 3 ~ 6 times, fully stir, carry out washing dechlorination, then Separation of Solid and Liquid, is precipitated thing and supernatant, described drying precipitate, remove magnetisable material with magnet, obtain dechlorination alkaline residue.
2. a kind of method removing chlorion in waste soda residue according to claim 1, is characterized in that, described magnetisable material is any one or a few in magnetic powder, magnetite powder or ground hematite.
3. a kind of method removing chlorion in waste soda residue according to claim 1, is characterized in that, described magnetisable material granularity is 2 ~ 10 μm.
4. a kind of method removing chlorion in waste soda residue according to claim 1, is characterized in that, described waste soda residue and magnetisable material mass ratio 100:0.5 ~ 1.
5. a kind of method removing chlorion in waste soda residue according to claim 1-4 any one, is characterized in that, when described waste soda residue carries out washing dechlorination, adopts the magnetostatic field of additional 4000 ~ 6000Gauss.
6. a kind of method removing chlorion in waste soda residue according to claim 1-4 any one, is characterized in that, described washing dechlorination mixing time is 0.5 ~ 1h.
7. a kind of method removing chlorion in waste soda residue according to claim 1-4 any one, is characterized in that, described solid-liquid separating method is standing separation method or leaves standstill-centrifugal process.
8. a kind of method removing chlorion in waste soda residue according to claim 1-4 any one, it is characterized in that, described drying means is natural drying method, the time is 4 ~ 5d.
9. a kind of method removing chlorion in waste soda residue according to claim 1-4 any one, is characterized in that, described waste soda residue, before washing dechlorination, carries out pretreatment, makes waste soda residue more than 90% granularity≤1mm.
10. a kind of method removing chlorion in waste soda residue according to claim 9, is characterized in that, described preprocess method is cal rolling method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510563512.3A CN105032903B (en) | 2015-09-08 | 2015-09-08 | Method for removing chloride ions in waste alkaline residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510563512.3A CN105032903B (en) | 2015-09-08 | 2015-09-08 | Method for removing chloride ions in waste alkaline residues |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105032903A true CN105032903A (en) | 2015-11-11 |
| CN105032903B CN105032903B (en) | 2017-04-12 |
Family
ID=54440204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510563512.3A Active CN105032903B (en) | 2015-09-08 | 2015-09-08 | Method for removing chloride ions in waste alkaline residues |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105032903B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186769A (en) * | 2016-07-15 | 2016-12-07 | 华南理工大学 | Preparation method and application are dried in a kind of alkaline residue water-retaining agent and revolution thereof |
| CN106186772A (en) * | 2016-07-15 | 2016-12-07 | 华南理工大学 | A kind of alkaline residue water-retaining agent and spray drying preparation thereof and application |
| CN106220018A (en) * | 2016-07-15 | 2016-12-14 | 华南理工大学 | Preparation method and application are dried in the revolution of a kind of inorganic particle water-retaining agent |
| CN106747300A (en) * | 2016-11-25 | 2017-05-31 | 潍坊天圣环保科技有限公司 | The method that inorganic filler is produced by alkaline residue white clay |
| CN114804794A (en) * | 2022-05-27 | 2022-07-29 | 路德环境科技股份有限公司 | Chloride ion curing agent for ammonia-soda process alkaline residue and preparation method and application thereof |
| CN114870493A (en) * | 2022-05-24 | 2022-08-09 | 青岛海湾化工设计研究院有限公司 | Recovery and treatment equipment for waste liquor in sodium carbonate production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070287A (en) * | 2010-12-03 | 2011-05-25 | 广州市天益三和能源环保有限公司 | Process for reducing chloride ions in white mud from ammonia soda plants |
| CN102557364A (en) * | 2011-12-30 | 2012-07-11 | 青岛碱业股份有限公司 | Method for reducing chloride ions in white mud of ammonia-alkali factory |
| CN104556523A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Method for treating alkali residue liquid waste and three-sludge of oil refineries |
-
2015
- 2015-09-08 CN CN201510563512.3A patent/CN105032903B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070287A (en) * | 2010-12-03 | 2011-05-25 | 广州市天益三和能源环保有限公司 | Process for reducing chloride ions in white mud from ammonia soda plants |
| CN102557364A (en) * | 2011-12-30 | 2012-07-11 | 青岛碱业股份有限公司 | Method for reducing chloride ions in white mud of ammonia-alkali factory |
| CN104556523A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Method for treating alkali residue liquid waste and three-sludge of oil refineries |
Non-Patent Citations (1)
| Title |
|---|
| 娄性义等: "《碱渣（白泥）综合利用途径的探讨》", 《青岛建筑工程学院学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186769A (en) * | 2016-07-15 | 2016-12-07 | 华南理工大学 | Preparation method and application are dried in a kind of alkaline residue water-retaining agent and revolution thereof |
| CN106186772A (en) * | 2016-07-15 | 2016-12-07 | 华南理工大学 | A kind of alkaline residue water-retaining agent and spray drying preparation thereof and application |
| CN106220018A (en) * | 2016-07-15 | 2016-12-14 | 华南理工大学 | Preparation method and application are dried in the revolution of a kind of inorganic particle water-retaining agent |
| CN106186769B (en) * | 2016-07-15 | 2019-01-15 | 华南理工大学 | A kind of alkaline residue water-retaining agent and its revolution drying preparation method and application |
| CN106186772B (en) * | 2016-07-15 | 2019-12-10 | 华南理工大学 | Alkali residue water-retaining agent and spray drying preparation method and application thereof |
| CN106747300A (en) * | 2016-11-25 | 2017-05-31 | 潍坊天圣环保科技有限公司 | The method that inorganic filler is produced by alkaline residue white clay |
| CN114870493A (en) * | 2022-05-24 | 2022-08-09 | 青岛海湾化工设计研究院有限公司 | Recovery and treatment equipment for waste liquor in sodium carbonate production |
| CN114870493B (en) * | 2022-05-24 | 2023-12-26 | 青岛海湾化工设计研究院有限公司 | Soda production waste liquid recovery processing equipment |
| CN114804794A (en) * | 2022-05-27 | 2022-07-29 | 路德环境科技股份有限公司 | Chloride ion curing agent for ammonia-soda process alkaline residue and preparation method and application thereof |
| CN114804794B (en) * | 2022-05-27 | 2022-12-13 | 路德环境科技股份有限公司 | Chloride ion curing agent for ammonia-soda process caustic sludge as well as preparation method and application of chloride ion curing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105032903B (en) | 2017-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105032903B (en) | Method for removing chloride ions in waste alkaline residues | |
| JP6404948B2 (en) | Method of preparing dechlorinated caustic sludge mixture from caustic sludge by ammonia soda method and its application | |
| Yang et al. | Investigating the synergistic effects of magnesia-coal slag based solid waste cementitious materials and its basic characteristics as a backfill material | |
| He et al. | Role of extracellular polymeric substances in enhancement of phosphorus release from waste activated sludge by rhamnolipid addition | |
| CN102092871A (en) | Method for reclaiming nitrogen and phosphorus in nitrogen and phosphorus-containing wastewater by using bittern as magnesium source | |
| CN102731001A (en) | Phosphogypsum composite pretreatment technique | |
| CN105537247A (en) | Method for curing arsenic-containing waste residues through industrial waste residues | |
| CN102674593A (en) | Method for treating waste water generated in ionic rare earth production | |
| CN109279745A (en) | A kind of method that biodegrade chelating agent couples electronic removal desulfurization wastewater sludge heavy-metal | |
| CN104445844A (en) | Method for dealkalizing red mud by uniting smoke and basic material | |
| CN106583415A (en) | Comprehensive utilization method for coal gangue components | |
| CN112875832B (en) | Preparation method of alkaline slow-release material | |
| CN106734146B (en) | Soil heavy metal pollution remediation method | |
| CN1986406A (en) | Production process of large grain anhydrous sodium sulfate with natural salt lake mirabilite | |
| Yu et al. | Leaching of phosphorus from phosphate tailings and extraction of calcium phosphates: Toward comprehensive utilization of tailing resources | |
| CN113633921A (en) | Fly ash dechlorination method | |
| CN115432714B (en) | Comprehensive utilization method of electrolytic manganese slag and demanganization building material | |
| Zong et al. | Research status of soda residue in the field of environmental pollution control | |
| CN103723854B (en) | Method for intensive recovery of phosphorus in phosphorus-rich wastewater through applying polyacrylamide | |
| CN110451531A (en) | A kind of fine purification treatment process of industrial waste salt containing organic matter of desalinization of soil by flooding or leaching combination in-situ oxidation | |
| CN105601022B (en) | A kind of method that high-quality Nacl is reclaimed in the waste water from Desulphurization for Coal-fired Power Plant | |
| CN113401928B (en) | Method for removing calcium from fly ash and/or coal gangue by acid washing with ultrasonic waves | |
| CN106244807B (en) | A method of the recovery purifying rare earth from ion adsorption type rare earth ore waste water | |
| CN112479232B (en) | Floatation separation method for industrial by-product sodium chloride and sodium sulfate | |
| CN108714481B (en) | method for extracting polyhalite from polyhalite ore containing gangue minerals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230601 Address after: 063300 Intersection of Chaoyang Street and Yingbin Road, Fengnan District, Tangshan City, Hebei Province Patentee after: Tangshan Ruihao Technology Co.,Ltd. Address before: 063009 Hebei province Tangshan City Xinhua West Road No. 46 Patentee before: NORTH CHINA University OF SCIENCE AND TECHNOLOGY |