CN113976098A - 一种废旧塑料热裂解用碱性催化剂的制备方法 - Google Patents
一种废旧塑料热裂解用碱性催化剂的制备方法 Download PDFInfo
- Publication number
- CN113976098A CN113976098A CN202111318632.9A CN202111318632A CN113976098A CN 113976098 A CN113976098 A CN 113976098A CN 202111318632 A CN202111318632 A CN 202111318632A CN 113976098 A CN113976098 A CN 113976098A
- Authority
- CN
- China
- Prior art keywords
- cacl
- solution
- catalyst
- thermal cracking
- filter cake
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 239000004033 plastic Substances 0.000 title claims abstract description 12
- 229920003023 plastic Polymers 0.000 title claims abstract description 12
- 239000002699 waste material Substances 0.000 title claims abstract description 10
- 238000004227 thermal cracking Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004537 pulping Methods 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000571 coke Substances 0.000 abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract 1
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- -1 alkali metal modified molecular sieve Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明公开了一种废旧塑料热裂解用碱性催化剂的制备方法,该催化剂具有层状结构,碱土金属改性后具有分布均匀的碱性中心,方便大分子的扩散,可减少生焦,是一种优良的热裂解用催化剂。
Description
技术领域:
本发明涉及一种废旧塑料热裂解用碱性催化剂的制备方法,属于碱性催化剂的范畴。
背景技术:
塑料制品方便了人民的生活,但随着使用量的增加,导致大量的旧塑料的产生,如何处理成为难题。目前市面上有各种处理塑料的方法。
其中废塑料热解主要包括热裂解法、催化热裂解法、热裂解-催化改质法,并且有不同的工艺。
通常所用的催化剂有固体硅酸铝、分子筛等,但在反应过程中大量的焦炭沉积于催化剂表面使其失活,而且反应温度>650℃,对催化剂的稳定性提出了更高得要求。
固体碱催化剂作为环境友好催化剂应用于废旧塑料催化热裂解工艺中有其优势,其分类有单组分金属氧化物、碱金属改性分子筛、载体负载碱金属离子。
钙基固体碱催化活性中心具有极强的供电子能力,近年来研究较多,但粉未状的氧化钙催化剂存在比表面小、易吸收空气中CO2致失活等特点。
我国每年废FCC催化剂在10万吨以上,近年来划为危险废物,其再生处埋主要采用磁分离技术和化学分离技术。磁分离利用Ni、Fe等金属的磁性以达到去除污染重的催化剂的目的,分离出污染较轻的催化剂用于平衡剂。该工艺电耗高、粉尘污染重、收率低。化学法主要使用酸浸,脱除部分金属,但程度不易控制。
发明内容:
本发明采用了以下技术方案:
(1)铝酸钠水溶液中并流加入CaCl2与MgCl2溶液,搅拌均匀后升温至60-90℃,静止陈化5-10小时过滤,洗涤,焙烧;
(2)将上述物料用水打浆,加入CaCl2溶液进行离子交换,过滤洗涤;
(3)滤饼用水打浆,加入硅溶胶,喷雾造粒,即得成品。
步骤(1)中的铝酸钠Na2O与Al2O3与质量比为(1.15-1.25)∶1。
步骤(1)中焙烧温度500-650℃,时间0.5-2小时。
步骤(1)中MgCl2的加入量以MgO计与以CaO计的CaCl2的质量比为1∶(8-15)。
步骤(2)中CaCl2的加入量以CaO计为滤饼干基质量的0.05~0.15。
步骤(3)中硅溶胶加入量以SiO2计占滤饼干基的4-8wt%。
本发明制备工艺具有以下特点与优势:
(1)铝酸钠与CaCl2、MgCl2混合后,在陈化过程中构建结构,形成了层状结构,焙烧掉氯根后,具有了适当的孔道;
(2)硅溶胶作为粘结剂,不提供酸性位,不具有活性,不会结焦堵塞孔道;
(3)CaCl2的交换,降低Na2O的含量,保证高温应用时稳定性。
具体实施方式:
以下对本发明的具体实施方式进行详细说明,应当理解的是此处所描述的具体实施不是为了限制本发明的范围。
本实施中所用原科的数据:
铝酸钠:Na2O120g/L,Al2O3100g/L;
CaCl2溶液:以CaO计,8wt%;
MgCl2溶液:以MgO计,7.5wt%;
硅溶胶:以SiO2计,25.0wt%。
实施例1:
(1)取1000mL的铝酸钠溶液,在搅拌的状态下,并流加入2175克CaCl2溶液与240克MgCl2溶液,搅拌均匀后,升温至85℃,陈化8小时,过滤,10倍水洗,滤饼烘干后550℃焙烧1小时;
(2)将该焙烧料加水打浆,加入292克CaCl2溶液进入离子交换,过滤洗涤;
(3)滤饼打浆,加入硅溶胶49克,喷雾干燥,样品标识为B-cat-1。
实施例2:
(1)取1000mL的铝酸钠溶液,在搅拌的状态下,并流加入2563克CaCl2溶液与209克MgCl2溶液,搅拌均匀后,升温至80℃,陈化10小时,过滤,10倍水洗,滤饼烘干后600℃焙烧1小时;
(2)将该焙烧料加水打浆,加入490克CaCl2溶液进入离子交换,过滤洗涤;
(3)滤饼打浆,加入硅溶胶105克,喷雾干燥,样品标识为B-cat-2。
实施例3:
(1)取1000mL的铝酸钠溶液,在搅拌的状态下,并流加入1725克CaCl2溶液与216克MgCl2溶液,搅拌均匀后,升温至65℃,陈化8小时,过滤,10倍水洗,滤饼烘干后550℃焙烧1小时;
(2)将该焙烧料加水打浆,加入238.1克CaCl2溶液进入离子交换,过滤洗涤;
(3)滤饼打浆,加入硅溶胶73克,喷雾干燥,样品标识为B-cat-3。
将废旧PP塑料粉碎成颗粒,每次进料1.5克,在自制的固定床裂解反应装置上进行评价,催化剂加剂量12克,反应温度700℃,产物分布如下:
从以上数据可以看出,其产物中乙烯+丙烯+丁烯,芳烃等高附加值产物较多,经济效益可观。
Claims (6)
1.一种废旧塑料热裂解用碱性催化剂的制备方法,具体步骤如下:
(1)铝酸钠水溶液中并流加入CaCl2与MgCl2溶液,搅拌均匀后升温至60-90℃,静止陈化5-10小时,过滤,洗涤,焙烧;
(2)将上述物料用水打浆,加入CaCl2溶液进行离子交换,过滤洗涤;
(3)滤饼用水打浆,加入硅溶胶,喷雾造粒,即得成品。
2.根据权利要求1所述的制备方法,其特征在于:步骤(1)中的铝酸钠Na2O与Al2O3的质量比为(1.15-1.25)∶1。
3.根据权利要求1所述的制备方法,其特征在于:步骤(1)中焙烧温度500-650℃,时间0.5-2小时。
4.根据权利要求1所述的制备方法,其特征在于:步骤(1)中MgCl2的加入量以MgO计与以CaO计的CaCl2的质量比为1∶(8-15)。
5.根据权利要求1所述的制备方法,其特征在于:步骤(2)中CaCl2的加入量以CaO计为滤饼干基质量的0.05-0.15。
6.根据权利要求1所述的制备方法其特征在于步骤(3)中硅溶胶加入量以SiO2计占滤饼干基的4-8wt%。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111318632.9A CN113976098B (zh) | 2021-11-09 | 2021-11-09 | 一种废旧塑料热裂解用碱性催化剂的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111318632.9A CN113976098B (zh) | 2021-11-09 | 2021-11-09 | 一种废旧塑料热裂解用碱性催化剂的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113976098A true CN113976098A (zh) | 2022-01-28 |
CN113976098B CN113976098B (zh) | 2024-02-13 |
Family
ID=79747298
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111318632.9A Active CN113976098B (zh) | 2021-11-09 | 2021-11-09 | 一种废旧塑料热裂解用碱性催化剂的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113976098B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115069295A (zh) * | 2022-07-18 | 2022-09-20 | 青岛惠城环保科技集团股份有限公司 | 一种催化裂解废料用催化剂的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107971015A (zh) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | 一种催化裂解催化剂及其制备方法 |
CN109304222A (zh) * | 2017-07-28 | 2019-02-05 | 中国石油天然气股份有限公司 | 一种裂化焦化蜡油多产液化气的催化裂化催化剂及其制备方法 |
CN109304210A (zh) * | 2017-07-28 | 2019-02-05 | 中国石油天然气股份有限公司 | 一种裂化焦化蜡油多产柴油的催化裂化催化剂制备方法 |
-
2021
- 2021-11-09 CN CN202111318632.9A patent/CN113976098B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107971015A (zh) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | 一种催化裂解催化剂及其制备方法 |
CN109304222A (zh) * | 2017-07-28 | 2019-02-05 | 中国石油天然气股份有限公司 | 一种裂化焦化蜡油多产液化气的催化裂化催化剂及其制备方法 |
CN109304210A (zh) * | 2017-07-28 | 2019-02-05 | 中国石油天然气股份有限公司 | 一种裂化焦化蜡油多产柴油的催化裂化催化剂制备方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115069295A (zh) * | 2022-07-18 | 2022-09-20 | 青岛惠城环保科技集团股份有限公司 | 一种催化裂解废料用催化剂的制备方法 |
CN115069295B (zh) * | 2022-07-18 | 2023-12-12 | 青岛惠城环保科技集团股份有限公司 | 一种催化裂解废料用催化剂的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN113976098B (zh) | 2024-02-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107857496B (zh) | 一种煤气化细渣的综合利用方法 | |
CN101423318B (zh) | 一种赤泥脱碱的方法 | |
CN108622904B (zh) | 利用煤气化细渣制备介孔微珠的方法及制得的介孔微珠 | |
CN102000599B (zh) | 一种深度脱除芳烃中微量烯烃催化剂的制备方法 | |
CN110624506B (zh) | 一种利用煤气化炉渣制备净水剂的方法及得到的净水剂 | |
CN101168117A (zh) | 利用电石渣浆制取高效固体脱硫剂的方法 | |
CN102491323A (zh) | 一种高脱硫活性焦的制备方法 | |
CN104248986A (zh) | 球形凹凸棒石介孔复合载体和负载型催化剂及其制备方法和应用以及乙酸乙酯的制备方法 | |
CN113976098A (zh) | 一种废旧塑料热裂解用碱性催化剂的制备方法 | |
CN111774045A (zh) | 一种硅藻土吸附剂的再生方法 | |
CN114195408A (zh) | 一种电石渣深度处理制备活性石灰的方法 | |
CN113184873B (zh) | 分子筛的制备方法、低氮气吸附的中空玻璃干燥剂及其制备方法 | |
WO2013125830A1 (ko) | 염산 및 폴리머를 이용하여 개질된 레드 머드를 제조하는 방법 | |
GB2622157A (en) | Wastewater adsorbent, and preparation method therefor and use thereof | |
CN114870908A (zh) | 一种废催化剂的综合利用方法 | |
US2430289A (en) | Process for ammoniating an acid treated clay | |
CN113731512A (zh) | 一种烃类催化裂解废催化剂的脱金属复活再利用方法 | |
CN113976132A (zh) | 一种废旧塑料热裂解用碱性催化剂的制备方法 | |
CN113101942A (zh) | 一种用于臭氧催化氧化的分子筛复合催化材料及其制备方法 | |
CN202173845U (zh) | 蒸汽冷凝水高温除铁陶瓷滤料 | |
CN111841485B (zh) | 一种碳化改性赤泥陶粒吸附剂的制备方法及其再生方法与应用 | |
CN112717961B (zh) | 滤渣及其制备方法以及催化裂化催化剂及其制备方法 | |
WO2012067291A1 (ko) | 철촉매의 제조방법 | |
CN108722423A (zh) | 一种生物质焦油裂解催化剂的制备方法 | |
CN110963501B (zh) | 高附加值x型分子筛及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
CB02 | Change of applicant information |
Address after: 266555 No.57, Huaihe East Road, Qingdao Economic and Technological Development Zone, Shandong Province Applicant after: Qingdao Huicheng Environmental Protection Technology Group Co.,Ltd. Address before: 266555 No.57, Huaihe East Road, Qingdao Economic and Technological Development Zone, Shandong Province Applicant before: QINGDAO HUI CHENG ENVIRONMENTAL TECHNOLOGY Co.,Ltd. |
|
CB02 | Change of applicant information | ||
GR01 | Patent grant | ||
GR01 | Patent grant |