CN104628013B - A kind of utilize the method for protein production ammonium carbonate in mud - Google Patents
A kind of utilize the method for protein production ammonium carbonate in mud Download PDFInfo
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- CN104628013B CN104628013B CN201510042672.3A CN201510042672A CN104628013B CN 104628013 B CN104628013 B CN 104628013B CN 201510042672 A CN201510042672 A CN 201510042672A CN 104628013 B CN104628013 B CN 104628013B
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- 238000000034 method Methods 0.000 title claims abstract description 27
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000001099 ammonium carbonate Substances 0.000 title claims abstract description 21
- 235000012501 ammonium carbonate Nutrition 0.000 title claims abstract description 21
- 230000014616 translation Effects 0.000 title claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 57
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 150000001413 amino acids Chemical class 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 27
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 12
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 12
- 230000009615 deamination Effects 0.000 claims abstract description 4
- 238000006481 deamination reaction Methods 0.000 claims abstract description 4
- 235000001014 amino acid Nutrition 0.000 claims description 38
- 239000010802 sludge Substances 0.000 claims description 23
- 238000000855 fermentation Methods 0.000 claims description 16
- 230000004151 fermentation Effects 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000010865 sewage Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 235000018102 proteins Nutrition 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 102000004316 Oxidoreductases Human genes 0.000 claims description 10
- 108090000854 Oxidoreductases Proteins 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 108091005804 Peptidases Proteins 0.000 claims description 8
- 239000004365 Protease Substances 0.000 claims description 8
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 8
- 230000017854 proteolysis Effects 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 102000005367 Carboxypeptidases Human genes 0.000 claims description 3
- 108010006303 Carboxypeptidases Proteins 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 238000007833 oxidative deamination reaction Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 3
- 238000006479 redox reaction Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000011499 joint compound Substances 0.000 claims description 2
- 229920001184 polypeptide Polymers 0.000 claims description 2
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 4
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000010801 sewage sludge Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000010354 integration Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 description 4
- 238000009264 composting Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000004715 keto acids Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
Landscapes
- Treatment Of Sludge (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a kind of method of protein production ammonium carbonate utilized in mud and technique for applying, relate to chemical technology field, especially relate to the technical field of sewage sludge harmlessness and disposal of resources. Its concrete technical scheme is: a kind of utilize the method for protein production ammonium carbonate in mud, it is characterized in that being hydrolyzed by the protein in mud by modifying agent effect, amino acid deamination and ammonia fixing, utilize fixing after the ammonium chloride that generates ammonium carbonate is synthesized with Paris white. A kind of method that the invention discloses sewage sludge harmlessness and recycling treatment, make full use of resource contained in mud, extracting ammonium carbonate from mud by Technology Integration conservative control reaction condition, the disposal for mud provides a kind of practicable new method.
Description
Technical field
The present invention is a kind of method of protein production ammonium carbonate utilized in mud, relates to chemical technology field, especially relates to town domestic sewage filter pressing sewage sludge harmlessness and resource treatment technique field.
Background technology
Along with the quick raising of China's level of urbanization and sewage treatment capacity, the by-product surplus sludge volume of sewage disposal is also in continuous growth. The mud total output of current urban wastewater treatment firm has reached 24,330,000 t/a, simultaneously with the speed increment of average annual 12%; Root is it was predicted that national urban wastewater treatment firm mud generation amount in 2015 is up to 60,000,000 t. If the mud of these enormous amount can not get effectively processing and disposing, pollutant can be made to be again introduced into water body through number of ways, cause sewage disposal meeting because Treatment of Sludge link causes huge economy and environmental cost. The Treatment of Sludge that China currently mainly applies and method of disposal have landfill, sludge incineration, sludge composting etc., and wherein landfill accounts for 63.0%, sludge composting accounts for 13.5%, mud nature mummification comprehensive utilization accounts for 5.4%, sludge incineration accounts for 1.8%, mud air storage and outward transport respectively account for 1.8% and 14.4%. It is true that the mud overwhelming majority of landfill, air storage and outward transport belongs to random disposal, really realize the ratio of safe disposal less than 20%; Mud need to other high heating value material mixed combustion because of moisture content height, and therefore sludge incineration is relatively costly; Mud can cause that in composting process the loss fertilizer efficiency of nitrogen element is relatively low, and there is the risk of heavy metal pollution. Conventional the pessimistic of sludge treating method effect makes whole Treatment of Sludge situation very severe.
Current China Treatment of Sludge and disposal are in serious hysteretic state, for the 20% ~ 30% of the investment Jin Zhan sewage treatment plant gross investment of sludge treatment, well below the ratio between investments (50% ~ 70%) of developed country." 12 " period, country starts to pay attention to the process handling problems of mud, carries out land resources science after encouraging development sewage sludge harmlessness, and state revenue puts into substantial contribution for Treatment of Sludge and disposal. " 12 " period, specific resistance to filtration market will be developed further, will become the next bright spot of investment after sewage disposal.
As can be seen here, China has a high potential on specific resistance to filtration, and Rapid development stage has been stepped in specific resistance to filtration market. Therefore, seeking a kind of new, specific resistance to filtration method effective, safety and environmental protection is a technical task urgent and urgently to be resolved hurrily to those skilled in the art.
Summary of the invention
For above-mentioned prior art Problems existing, the invention provides and a kind of simple and effective utilize the method for protein production ammonium carbonate in mud, provide a feasibility road for sewage treatment plant sludge harmless and disposal of resources. Concrete technical scheme is: a kind of method of protein production ammonium carbonate utilized in mud, and it is characterized in that and is realized by the steps: the proteolysis in the mud of sewage treatment plant's output is become free aminoacid; Aminoacid deaminizating under amino acid oxidase effect generates ammonia; Then through the conversion of ammonia with fixing, namely ammonia and water generate ammonium hydroxide, and the iron chloride, the aluminium reaction that exist in ammonium hydroxide and mud generate ammonium chloride; Ammonium chloride and the Paris white carbonate synthesis ammonium in a heated condition more than 300 orders.
In order to better implement the present invention, its scheme can also further specifically be refined as:
It is furthermore that the described modifying agent that utilizes the degradation of proteins into free aminoacid process is: heap fermentation the mud of moisture content 80% and modifying agent being sufficiently mixed in modified ditch after uniformly, stacking and be highly maintained at about 80cm, modifying agent adding proportion is the one thousandth of mud gross weight to be modified; In modified first 48-96 hour, on average carried out turning over buttress every 8 hours, be beneficial to sludge water content volatilization; When outside air temperature T >=20 DEG C, after fermenting 24 hours, mud temperature is up to more than 40 DEG C, under the catalytic action of the protease in modifying agent, the protein of macromole becomes more micromolecular polypeptide, continue fermentation, protein in mud becomes peptide and the part free amino acid of short chain under the effect of enzyme, and mud, through the fermentation of 48 hours, is finally all transformed into free amino acid under the synergism of carboxypeptidase and protease.
It is furthermore that described aminoacid deaminizating under amino acid oxidase effect generates the process of ammonia and is: mud and modifying agent mixing are fermented under the effect of protease, protein in mud occurs hydrolysis to generate aminoacid, turning over buttress at machinery and provide under Oxygen Condition, aminoacid occurs oxidative deamination reaction to take off amino under the effect of amino acid oxidase; Under anoxic conditions, there is mutually oxidation-reduction reaction in two aminoacid, generates organic acid, keto acid and ammonia.
The conversion being furthermore that described ammonia with fixing process is: sludge fermentation 72-96 hour, fermentation temperature T �� 40-50 DEG C, pH �� 6.0-6.5 when, the water reaction reacted in the ammonia and mud generated through proteolysis, amino acid deamination in mud generates ammonium hydroxide, ferric chloride and aluminum chloride reaction in wherein most ammonium hydroxide and mud generate ammonium chloride, it is achieved fixing of ammonia.
It is furthermore that described ammonium chloride and more than the Paris white carbonate synthesis ammonium in a heated condition of 300 orders is: the nitrogen in mud is fixed as after ammonium chloride through serial reaction, mud continues fermentation heat production, buttress mummification is turned over through machinery, when moisture content in mud drops to 25-30%, the Paris white more than 300 orders accounting for mud gross weight 1-3% is added in mud, heat to mud temperature through machinery and reach more than 100 DEG C, ammonium chloride in mud and Paris white reaction generate the mixed vapour of ammonium carbonate and water, cooled obtain ammonium carbonate crystal.
Technical scheme make use of the various resources in mud fully, rational reaction condition and response time are provided by Technology Integration, nitrogen in protein contained by mud is eventually converted into ammonia through sequence of chemical reaction, and the generation ammonium carbonate that is used, it is achieved that the disposal of resources of mud. Nitrogen in mud has carried out conversion, has fixed, and namely avoids the environmental pollution that atmospheric environment is caused because of the discharge of nitrogen oxides in sweat by mud, can produce again ammonium carbonate commodity, it is achieved recycling sludge is disposed.
Detailed description of the invention
A kind of method of protein production ammonium carbonate utilized in mud, is realized by the steps: the proteolysis in the mud of sewage treatment plant's output is become free aminoacid; Aminoacid deaminizating under amino acid oxidase effect generates ammonia; Then through the conversion of ammonia with fixing, namely ammonia and water generate ammonium hydroxide, and the iron chloride, the aluminium reaction that exist in ammonium hydroxide and mud generate ammonium chloride; Ammonium chloride and the Paris white carbonate synthesis ammonium in a heated condition more than 300 orders.
Its processing step can be specific as follows:
A, build sludge modification ditch: build sludge modification ditch, be mainly used in mud turn over buttress, modified, modifiy ditch specification and determine according to sludge quantity to be modified and production scale.
B, sludge modification: heap fermentation after the mud of the moisture content 80% of sewage treatment plant's output and modifying agent medicine being sufficiently mixed in modified ditch, mud is stacked and is highly maintained at about 80cm. When outside air temperature T >=20 DEG C, after fermenting 24 hours, temperature is up to more than 40 DEG C, and under preference temperature, the protein in mud starts hydrolysis, and after continuing 24 hours, protein can all be hydrolyzed to aminoacid; The aminoacid being hydrolyzed generation after fermenting 48 hours starts desamination reaction, and this process need to be piled up neatly equipment with automatic turning and mud is repeatedly turned over buttress, the aerobic environment required to ensure reaction; Aminoacid deaminizating under amino acid oxidase effect generates the process of ammonia and is: mud and modifying agent mixing are fermented under the effect of protease, protein in mud occurs hydrolysis to generate aminoacid, turn over buttress at machinery and provide under Oxygen Condition, aminoacid occurs oxidative deamination reaction to take off amino under the effect of amino acid oxidase, often consumes 1 molecular oxygen and produces 2 molecule 2-ketoacids and 2 molecules of ammonia. Its chemical equation is:
Under anoxic conditions, there is mutually oxidation-reduction reaction in two aminoacid, generates organic acid, keto acid and ammonia, and reaction equation is as follows:
The conversion of ammonia and fixing process be sludge fermentation 72-96 hour, fermentation temperature T �� 40-50 DEG C, pH �� 6.0-6.5 when, the water reaction reacted in the ammonia and mud generated through proteolysis, amino acid deamination in mud generates ammonium hydroxide, wherein the ferric chloride in ammonium hydroxide and mud and aluminum chloride reaction generate ammonium chloride, realizing the fixing of ammonia, reaction equation is as follows:
Fermentation, modifiied after moisture percentage in sewage sludge can be reduced to about 25%.
C, the synthesis of ammonium carbonate and extraction: modified mud will be passed through and be sufficiently mixed more than the Paris white of 300 orders in step B, nitrogen in mud is after reaction is fixed as ammonium chloride, mud continues fermentation heat production, buttress mummification is turned over through machinery, when moisture content in mud drops to 25-30%, the Paris white more than 300 orders accounting for mud gross weight 1-3% is added in mud, heat to mud temperature through machinery and reach more than 100 DEG C, ammonium chloride and Paris white in mud react the mixed vapour generating ammonium carbonate and water, mixed vapour enters cooling system cooling under the effect of air-introduced machine, ammonium carbonate crystal is obtained after cooled separation, its chemical equation is as follows:
The modifying agent main component used in the present invention has: the plant seed warp broken effective ingredient that propose high containing fat and magnesium carbonate, organic nutrition source, yeast flora and carboxypeptidase, protease and amino acid oxidase.
Claims (2)
1. the method for the protein production ammonium carbonate that a kind utilizes in mud, it is characterised in that realized by the steps: the proteolysis in the mud of sewage treatment plant's output is become free aminoacid; Aminoacid deaminizating under amino acid oxidase effect generates ammonia; Then through the conversion of ammonia with fixing, namely ammonia and water generate aqua ammonia, and the iron chloride, the aluminium reaction that exist in aqua ammonia and mud generate ammonia chloride; Ammonium chloride and the Paris white carbonate synthesis ammonium in a heated condition more than 300 orders; Described is free amino acid process by proteolysis in mud is: the mud of the moisture content 80% of sewage treatment plant's output and modifying agent rise after Homogeneous phase mixing heap fermentation in modified ditch, and mud is stacked and is highly maintained at about 80cm; When ambient temperature is maintained at more than 20 DEG C, after 24 hours fermentation, mud temperature is up to more than 40 DEG C, and in modifying agent under the catalytic action of protease, the protein in mud occurs hydrolysis to generate polypeptide; After fermenting 48 hours, under the synergism of carboxypeptidase and protease, protein is finally hydrolyzed to free aminoacid; The conversion of described ammonia with fixing process is: sludge fermentation 72-96 hour, fermentation temperature T=40-50 DEG C, pH=6.0-6.5 when, the water reaction reacted in the ammonia and mud generated through proteolysis, amino acid deamination in mud generates ammonium hydroxide, wherein the ferric chloride in ammonium hydroxide and mud and aluminum chloride reaction generate ammonium chloride, it is achieved ammonia fixing; Described ammonium chloride with more than the Paris white carbonate synthesis ammonium in a heated condition of 300 orders be: the nitrogen in mud through reaction be fixed as ammonium chloride after, mud continues fermentation heat production, buttress mummification is turned over through machinery, when moisture content in mud drops to 25-30%, the Paris white more than 300 orders accounting for mud gross weight 1-3% is added in mud, heat to mud temperature through machinery and reach more than 100 DEG C, ammonium chloride in mud and Paris white reaction generate the mixed vapour of ammonium carbonate and water, cooled obtain ammonium carbonate crystal.
2. the method for the protein production ammonium carbonate utilized in mud according to claim 1, it is characterized in that described aminoacid deaminizating under amino acid oxidase effect generates the process of ammonia and is: mud and modifying agent mixing are fermented under the effect of protease, protein in mud occurs hydrolysis to generate aminoacid, turning over buttress at machinery and provide under Oxygen Condition, aminoacid occurs oxidative deamination reaction to take off amino under the effect of amino acid oxidase;Under anoxic conditions, there is mutually oxidation-reduction reaction in two aminoacid, generates organic acid and ammonia.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008143914A1 (en) * | 2007-05-16 | 2008-11-27 | The University Of Maryland, College Park | Novel methods for recovery of leaf proteins |
| CN102452719A (en) * | 2010-11-04 | 2012-05-16 | 美舒环保科技（北京）有限公司 | Preparation method of compound microelement nutrient capable of enhancing activity of activated sludge |
| CN104271535A (en) * | 2012-02-03 | 2015-01-07 | 优尼缇化肥有限责任公司 | Systems and methods for converting and processing organic sludges for multi-nutrient single accreted granule enhanced efficiency fertilizer production |
-
2015
- 2015-01-28 CN CN201510042672.3A patent/CN104628013B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008143914A1 (en) * | 2007-05-16 | 2008-11-27 | The University Of Maryland, College Park | Novel methods for recovery of leaf proteins |
| CN102452719A (en) * | 2010-11-04 | 2012-05-16 | 美舒环保科技（北京）有限公司 | Preparation method of compound microelement nutrient capable of enhancing activity of activated sludge |
| CN104271535A (en) * | 2012-02-03 | 2015-01-07 | 优尼缇化肥有限责任公司 | Systems and methods for converting and processing organic sludges for multi-nutrient single accreted granule enhanced efficiency fertilizer production |
Non-Patent Citations (1)
| Title |
|---|
| 污水处理厂污泥的再利用集成技术;李亚东，李海波，梁浩;《环境污染治理技术与设备》;20050531;第6卷(第5期);全文 * |
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Effective date of registration: 20191210 Address after: 264009 No.2 Kunlunshan Road, Yantai Economic and Technological Development Zone, Shandong Province Patentee after: Shandong Yiyuan green carbon environmental protection technology Co., Ltd Address before: 264000 Xu village, Peach Town, Qixia, Shandong, Yantai Patentee before: Xu Minghao |