CN105505453A - Water-free coal tar desalting and demetalization method - Google Patents

Water-free coal tar desalting and demetalization method Download PDF

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Publication number
CN105505453A
CN105505453A CN201610028928.XA CN201610028928A CN105505453A CN 105505453 A CN105505453 A CN 105505453A CN 201610028928 A CN201610028928 A CN 201610028928A CN 105505453 A CN105505453 A CN 105505453A
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Prior art keywords
coal tar
solid
auxiliary agent
impurity
mixing
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CN201610028928.XA
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CN105505453B (en
Inventor
房广信
李志英
何宏鹰
房振达
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SHENZHEN QIANHAI XINYU ENERGY TECHNOLOGY CO., LTD.
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Maoming Yingpeng Electromechanical Equipment Co Ltd
Shenzhen Qianhai Xinyu Energy Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00Treatment of hydrocarbon oils in the absence of hydrogen, by two or more refining processes
    • C10G53/02Treatment of hydrocarbon oils in the absence of hydrogen, by two or more refining processes plural serial stages only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/205Metal content

Abstract

The invention relates to the technical field of coal chemical industry and particularly discloses a water-free coal tar desalting and demetalization method. The method comprises the following sequential steps: heating treatment, first auxiliary adding and mixing, first-level solid-liquid separation, second auxiliary adding and mixing and second-level solid-liquid separation. In the method disclosed by the invention, water injection is not needed, special auxiliaries are added into coal tar containing lots of impurities, and proper stirring mixing is performed so that the impurities collide with each other for coalescence; and after that, solid-liquid separation equipment is adopted for two levels of effective separation so as to obtain the coal tar of which the purifying rate reaches 93-97% and the yield after the purification reaches 95-97%. The method disclosed by the invention has the advantages of novel technology, simple equipment and easiness in operation and can realize continuous separation.

Description

A kind of coal tar is without the demetallated method of water desalination
Technical field
The present invention relates to technical field of coal chemical industry, be specifically related to a kind of coal tar without the demetallated method of water desalination.
Background technology
Coal tar is with bituminous coal and brown coal for raw material, and producing the byproduct that semicoke process produces, is 5 ~ 10% of raw coal in its output of China.In all kinds of coal tar, all contain to production equipment that particularly hydrogenation production unit, hydrogenation catalyst and quality product work the mischief or produce dysgenic impurity; These impurity are moisture (1.5 ~ 4.5%) mainly, metal (100 ~ 400 ㎎/㎏) and solid impurity (1 ~ 5%).Water in coal tar can cause furnace operation temperature fluctuation, increases energy consumption; Cause equipment pressure change after moisture vaporization, water vapour makes catalyst aging and activity decrease or makes its efflorescence, blocking hydrogenator.If master metal sodium, calcium, magnesium, iron, nickel, copper, arsenic etc. contained in coal tar, these metals not only can cause damage to hydrogenation production unit and pipeline, and serious even also can make hydrogenation catalyst poisoning and inactivation.Solid impurity in coal tar mainly fine breeze, coke powder, carbon black and pyrolysis product thermopolymerization forms macromole aromatic polymer etc., these solid impurities can cause Severe blockage to hydrogenation production unit and pipeline, especially Severe blockage can be caused to hydrogenator bed, therefore, purifying treatment must be carried out to coal tar in producing fuel oil by coal tar hydrogenation modifying process.
For many years, domestic and international many people have employed settlement separate, multiple separation method and the technology such as centrifugation, electric field purification (electrical desalting and dewatering device), chemical separation, solvent extraction, cyclonic separation, filtering separation, all fail to address this problem well.All there is the defects such as inferior separating effect, efficiency is low in these separation methods and technology, and maximum problem be existing separation method and technology all cannot by the impurity in coal tar, especially metallic element (sodium, calcium, magnesium, iron, nickel, copper, arsenic) forms solid-state separating, purification separation weak effect, efficiency are low, can not meet the specification of quality of subsequent production device to coal tar.
Summary of the invention
In view of this, be necessary for above-mentioned problem, provide a kind of coal tar without the demetallated method of water desalination, to solve existing separation method weak effect, inefficient problem.
For achieving the above object, the present invention takes following technical scheme:
A kind of coal tar, without the demetallated method of water desalination, comprising:
Step 1 heat treated: adopt heat exchanger that the coal tar containing impurity is heated to 100 ~ 200 DEG C in mixing tank;
Step 2 first time adds agent mixing: in mixing tank, add X auxiliary agent, and carry out mix and blend 10 ~ 60 minutes, make impurity mutually collide polymerization;
Step 3 first step solid-liquid separation: adopt solid-liquid separating equipment to be separated the coal tar after processing through step 2, thus obtain remove partial impurities partly purify coal tar;
Step 4 second time adds agent mixing: half purification coal tar is placed in mixing tank and adds Y auxiliary agent, mix and blend 10 ~ 60 minutes, makes the mutual collision coalescence of impurity;
Step 5 second stage solid-liquid separation: adopt solid-liquid separating equipment to be separated the half purification coal tar processed through step 4, thus obtain the purification coal tar of complete imurity-removal.
Further, described X auxiliary agent is selected from monocarboxylic acid, di-carboxylic acid, organic phosphoric acid, amino acid and derivative thereof, at least one in polyphosphoric acid or hydroxyquinoline, described Y auxiliary agent is selected from least one in the polymkeric substance of single methanol or glycol, quaternary ammonium salt, quaternary alkylphosphonium salt or crown ether.
Further, total add-on of described auxiliary agent is 200 ~ 5000 ㎎/㎏; Wherein X promoter addition is 120 ~ 3800 ㎎/㎏, and Y promoter addition is 80 ~ 1200 ㎎/㎏.
Further, step 2 and the stirring described in step 4 are complete random mixed flow for coal tar is stirred to form, and described flow velocity is 10 ~ 50 meter per seconds.
Compared with prior art beneficial effect of the present invention is:
(1) the inventive method technology is novel, equipment is simple, processing ease, can realize being continuously separated.
(2) the present invention does not need water filling, in the coal tar containing a large amount of impurity, add special auxiliary agent, and carry out mixed with moderate agitation, make the mutual collision coalescence of impurity, then adopt solid-liquid separating equipment to be effectively separated, thus deimpurity purification coal tar is removed in acquisition.
(3) impurity in coal tar is with the form fractionation of solid slag out; Adopt solid-liquid separating equipment to carry out solid-liquid separation, speed is fast, effective, and coal tar purification rate reaches 93 ~ 97%, and the coal tar yield after purification reaches 95 ~ 97%.
(4) purify coal tar as the raw material of hydrogenation unit, significantly can reduce equipment manufacturing cost and the loaded catalyst of device, extend on-stream time, reduce production cost.
(5) two-stage solid-liquid separation solid slag out can be used as fuel and coal mixes burning, and desalination demetalization process does not need water filling, does not produce sewage, environmentally friendly.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of coal tar of the present invention without the demetallated method of water desalination.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with the embodiment of the present invention, do to describe clearly and completely further to technical scheme of the present invention.It should be noted that, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
As shown in Figure 1, a kind of coal tar, without the demetallated method of water desalination, comprising:
Step 1 heat treated: adopt heat exchanger that the coal tar containing impurity is heated to 100 ~ 200 DEG C in mixing tank;
Step 2 first time adds agent mixing: in mixing tank, add X auxiliary agent, and carry out mix and blend 10 ~ 60 minutes, make impurity mutually collide polymerization; Described X auxiliary agent is selected from monocarboxylic acid, di-carboxylic acid, organic phosphoric acid, amino acid and derivative thereof, at least one in polyphosphoric acid or hydroxyquinoline;
Step 3 first step solid-liquid separation: adopt solid-liquid separating equipment to be separated the coal tar after processing through step 2, thus obtain remove partial impurities partly purify coal tar;
Step 4 second time adds agent mixing: half purification coal tar is placed in mixing tank and adds Y auxiliary agent, mix and blend 10 ~ 60 minutes, makes the mutual collision coalescence of impurity; Described Y auxiliary agent is selected from least one in the polymkeric substance of single methanol or glycol, quaternary ammonium salt, quaternary alkylphosphonium salt or crown ether;
Step 5 second stage solid-liquid separation: adopt solid-liquid separating equipment to be separated half purification coal tar after step 4 process, thus obtain the purification coal tar of complete imurity-removal.
Preferably, total add-on of described auxiliary agent is 200 ~ 5000 ㎎/㎏; Wherein X promoter addition is 120 ~ 3800 ㎎/㎏, and Y promoter addition is 80 ~ 1200 ㎎/㎏.
Preferably, step 2 and the stirring described in step 4 are complete random mixed flow for coal tar is stirred to form, and its flow velocity is 10 ~ 50 meter per seconds.
The coal tar purification rate that the present invention obtains reaches 93 ~ 97%, and yield reaches 95 ~ 97%.
Embodiment 1
Step 1 heat treated: adopt heat exchanger that the coal tar containing impurity is heated to 100 DEG C in mixing tank;
Step 2 first time adds agent mixing: the X auxiliary agent adding 4000 ㎎/㎏ in mixing tank, and wherein di-carboxylic acid accounts for 40%, and organic phosphoric acid accounts for 60%; Appropriateness stirs and makes coal tar form complete random mixed flow, and flow velocity 45 meter per second, stirs 40 minutes, make the mutual collision coalescence of impurity;
Step 3 first time solid-liquid separation: adopt solid-liquid separating equipment to be separated the coal tar after processing through step 2, thus obtain remove partial impurities partly purify coal tar;
Step 4 second time adds agent mixing: half purification coal tar is placed in mixing tank and adds the Y auxiliary agent of 500 ㎎/㎏, and wherein diol polymer accounts for 65%, and quaternary ammonium salt accounts for 35%; Appropriateness stirs and makes coal tar form complete random mixed flow, and flow velocity 20 meter per second, stirs 30 minutes, make the mutual collision coalescence of impurity;
Step 5 second time solid-liquid separation: adopt solid-liquid separating equipment to be separated half purification coal tar after step 4 process, thus obtain the purification coal tar of complete imurity-removal.
Embodiment 2
Step 1 heat treated: adopt heat exchanger that the coal tar containing impurity is heated to 150 DEG C in mixing tank;
Step 2 first time adds agent mixing: the X auxiliary agent adding 3000 ㎎/㎏ in mixing tank, and wherein di-carboxylic acid accounts for 40%, and organic phosphoric acid accounts for 60%, appropriateness stirs and makes coal tar form complete random mixed flow, flow velocity 35 meter per second, stirs 30 minutes, makes the mutual collision coalescence of impurity;
Step 3 first step solid-liquid separation: adopt solid-liquid separating equipment to be separated the coal tar after processing through step 2, thus obtain remove partial impurities partly purify coal tar;
Step 4 second time adds agent mixing: half purification coal tar is placed in mixing tank and adds the Y auxiliary agent of 1000 ㎎/㎏, wherein diol polymer accounts for 65%, quaternary ammonium salt accounts for 35%, appropriateness stirs and makes coal tar form complete random mixed flow, flow velocity 25 meter per second, stir 20 minutes, make the mutual collision coalescence of impurity;
Step 5 second stage solid-liquid separation: adopt solid-liquid separating equipment to be separated half purification coal tar after step 4 process, thus obtain the purification coal tar of complete imurity-removal.
Embodiment 3
Step 1 heat treated: adopt heat exchanger that the coal tar containing impurity is heated to 200 DEG C in mixing tank;
Step 2 first time adds agent mixing: the X auxiliary agent adding 2000 ㎎/㎏ in mixing tank, and wherein di-carboxylic acid accounts for 40%, and organic phosphoric acid accounts for 60%, appropriateness stirs and makes coal tar form complete random mixed flow, flow velocity 25 meter per second, stirs 30 minutes, makes the mutual collision coalescence of impurity;
Step 3 first time solid-liquid separation: adopt solid-liquid separating equipment to be separated the coal tar after processing through step 2, thus obtain remove partial impurities partly purify coal tar;
Step 4 second time adds agent mixing: half purification coal tar is placed in mixing tank and adds the Y auxiliary agent of 1500 ㎎/㎏, wherein diol polymer accounts for 65%, quaternary ammonium salt accounts for 35%, appropriateness stirs and makes coal tar form complete random mixed flow, flow velocity 30 meter per second, stir 30 minutes, make the mutual collision coalescence of impurity;
Step 5 second time solid-liquid separation: adopt solid-liquid separating equipment to be separated half purification coal tar after step 4 process, thus obtain the purification coal tar of complete imurity-removal.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (4)

1. coal tar is without the demetallated method of water desalination, it is characterized in that, comprising:
Step 1 heat treated: adopt heat exchanger that the coal tar containing impurity is heated to 100 ~ 200 DEG C in mixing tank;
Step 2 first time adds agent mixing: in mixing tank, add X auxiliary agent, and carry out mix and blend 10 ~ 60 minutes, make impurity mutually collide polymerization;
Step 3 first step solid-liquid separation: adopt solid-liquid separating equipment to be separated the coal tar after processing through step 2, thus obtain remove partial impurities partly purify coal tar;
Step 4 second time adds agent mixing: half purification coal tar is placed in mixing tank and adds Y auxiliary agent, mix and blend 10 ~ 60 minutes, makes the mutual collision coalescence of impurity;
Step 5 second stage solid-liquid separation: adopt solid-liquid separating equipment to be separated the half purification coal tar processed through step 4, thus obtain the purification coal tar of complete imurity-removal.
2. coal tar according to claim 1 is without the demetallated method of water desalination, it is characterized in that, described X auxiliary agent is selected from monocarboxylic acid, di-carboxylic acid, organic phosphoric acid, amino acid and derivative thereof, at least one in polyphosphoric acid or hydroxyquinoline, described Y auxiliary agent is selected from least one in the polymkeric substance of single methanol or glycol, quaternary ammonium salt, quaternary alkylphosphonium salt or crown ether.
3. coal tar according to claim 1 and 2 is without the demetallated method of water desalination, it is characterized in that, total add-on of described auxiliary agent is 200 ~ 5000 ㎎/㎏; Wherein X promoter addition is 120 ~ 3800 ㎎/㎏, and Y promoter addition is 80 ~ 1200 ㎎/㎏.
4. coal tar according to claim 1 is without the demetallated method of water desalination, it is characterized in that, step 2 and the stirring described in step 4 are complete random mixed flow for coal tar is stirred to form, and described flow velocity is 10 ~ 50 meter per seconds.
CN201610028928.XA 2016-01-15 2016-01-15 A kind of coal tar is without the demetallated method of water desalination Active CN105505453B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107603654A (en) * 2016-07-11 2018-01-19 中国石油化工股份有限公司 The process for demetalizating of coal tar and the catalytic hydrogenation method of coal tar and system
CN110157478A (en) * 2018-02-11 2019-08-23 中国石油化工股份有限公司 A kind of preprocess method of coal tar raw material
CN112011362A (en) * 2019-05-31 2020-12-01 中国石油化工股份有限公司 Method for removing sodium salt from hydrocarbon oil

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02199192A (en) * 1988-11-30 1990-08-07 Inst Chem Przemyslowej Method for separation and purification of coal-tar-derived anthracene
CN101619229A (en) * 2008-07-04 2010-01-06 汉能科技有限公司 Method for preparing diesel oil components with coal tar oil light ends
CN103937531A (en) * 2014-03-27 2014-07-23 中国石油天然气集团公司 Chemical pretreatment agent and pretreatment method for coal tar

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02199192A (en) * 1988-11-30 1990-08-07 Inst Chem Przemyslowej Method for separation and purification of coal-tar-derived anthracene
CN101619229A (en) * 2008-07-04 2010-01-06 汉能科技有限公司 Method for preparing diesel oil components with coal tar oil light ends
CN103937531A (en) * 2014-03-27 2014-07-23 中国石油天然气集团公司 Chemical pretreatment agent and pretreatment method for coal tar

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107603654A (en) * 2016-07-11 2018-01-19 中国石油化工股份有限公司 The process for demetalizating of coal tar and the catalytic hydrogenation method of coal tar and system
CN107603654B (en) * 2016-07-11 2020-01-10 中国石油化工股份有限公司 Demetallization method of coal tar and catalytic hydrogenation method and system of coal tar
CN110157478A (en) * 2018-02-11 2019-08-23 中国石油化工股份有限公司 A kind of preprocess method of coal tar raw material
CN110157478B (en) * 2018-02-11 2021-04-06 中国石油化工股份有限公司 Pretreatment method of coal tar raw material
CN112011362A (en) * 2019-05-31 2020-12-01 中国石油化工股份有限公司 Method for removing sodium salt from hydrocarbon oil
CN112011362B (en) * 2019-05-31 2022-03-11 中国石油化工股份有限公司 Method for removing sodium salt from hydrocarbon oil

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