CN102020567B - Method and device for refining coarse nitrobenzene - Google Patents
Method and device for refining coarse nitrobenzene Download PDFInfo
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- CN102020567B CN102020567B CN 200910195530 CN200910195530A CN102020567B CN 102020567 B CN102020567 B CN 102020567B CN 200910195530 CN200910195530 CN 200910195530 CN 200910195530 A CN200910195530 A CN 200910195530A CN 102020567 B CN102020567 B CN 102020567B
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Abstract
The invention provides a method and a device for refining coarse nitrobenzene. The method comprises the following steps that: firstly, the coarse nitrobenzene is preheated by a pipe heat exchanger and enters a stripping tower, and volatile benzene is dissolved in water vapor and is discharged from a tower top to complete debenzolization; secondly, the debenzolized nitrobenzene enters a phase separator, and water in the dispersed state is subjected to coagulation and sedimentation in the phase separator and is discharged from a light phase opening, so that the purity of the nitrobenzene removed from a heavy phase opening is 99.5 percent; and finally, the nitrobenzene of which the purity is 99.5 percent is conveyed to a molecular sieve packed tower to refine the coarse nitrobenzene, wherein a molecular sieve has the characteristic of adsorbing polar molecules selectively, and after water molecules are adsorbed, the purity of the nitrobenzene is over 99.99 percent. The method and the device overcome the defect of the conventional rectification for refining the coarse nitrobenzene, have the advantages of operation safety and high separation accuracy, and open up a new concept for the refining of the coarse nitrobenzene in the chemical production of the nitrobenzene.
Description
Technical field
The present invention relates to a kind of for thick oil of mirbane process for purification and device, particularly a kind of thick oil of mirbane process for purification and device thereof in the oil of mirbane Chemical Manufacture.
Background technology
Oil of mirbane is mainly used in synthetic important Organic Chemicals aniline, at present domesticly build separately nitrobenzene plant except enterprise of 1-2 family, all the other are all supporting with Aniline Unit, and most of ability is arranged in pairs or groups substantially, except a small amount of solvent, reagent, field of fine chemical were used, the commodity amount of oil of mirbane was very little, but along with the exploitation of derived product, the non-aniline consumption of oil of mirbane constantly enlarging, has good development prospect in recent years.
At present, mixed acid nitrifying is mainly adopted in oil of mirbane production, comprises nitrated, concentrated, washing, refining four steps.Traditional process for purification adopts rectifying, thick oil of mirbane enters primary tower after preheating, the primary tower negative pressure (0.07Mpa) steams benzene and water, the high boiling material material enters rectifying tower (negative pressure-0.09Mpa) at the bottom of the tower of primary tower, the tower top of rectifying tower steams the oil of mirbane finished product, and tower bottoms is called tar.Traditional thick oil of mirbane process for purification rectifying needs very harsh operational condition, and the accident of blasting repeatedly, and the explosion cause of report comprises at present: the many nitro-compounds of the by product that 1. produces in nitrifying process decompose in rectifying tower; 2. the nitro phenates that produces in washing process deposits in reboiler; When 3. rectifying tower stopped, air entered and causes the tar blast.In addition, the thick oil of mirbane tradition process for purification drawbacks such as also the prodigiosin consumption is high, by product is many.In view of there is above defective in thick oil of mirbane tradition process for purification, the applicant has developed the method refining crude oil of mirbane that utilizes stripping tower, phase separator and the combination of molecular sieve filling tower.
Summary of the invention
One of technical problem to be solved by this invention is to overcome the deficiency of prior art, a kind of thick oil of mirbane process for purification is provided, adopt the method refining crude oil of mirbane, have advantages of that operational safety, separation accuracy are high, have opened up a kind of new approaches for thick oil of mirbane in the oil of mirbane Chemical Manufacture is refining.
Two of technical problem to be solved by this invention is to provide a kind of thick oil of mirbane refining device.
As a kind of thick oil of mirbane process for purification of first aspect present invention, it comprises the following steps:
(a) at first thick oil of mirbane enter stripping tower after the tubular heat exchanger preheating, and volatile component benzene is discharged from the tower top of stripping tower with water vapor, and the oil of mirbane that takes off after benzene enters phase separator at the bottom of the tower of stripping tower;
(b) oil of mirbane that takes off after benzene is purified in phase separator again, and the water of dispersed enters blowdown pipeline carry out flocking settling in phase separator after, and the oil of mirbane of heavy phase product 99.5% enters the molecular sieve filling tower;
(c) micro-moisture in molecular sieve filling tower selective adsorption nitrobenzene solution, the oil of mirbane purity after absorption are completed the refining of thick oil of mirbane at this more than 99.99%;
(d) oil of mirbane after refining enters product storage tank and stores.
As the thick oil of mirbane refining plant of second aspect present invention, it comprises:
A. a tubular heat exchanger that is used for the thick oil of mirbane of preheating, be provided with thick nitrobenzene feed mouth, thick oil of mirbane discharge port, hot-fluid import, hot-fluid outlet; Wherein thick oil of mirbane is entered in tubular heat exchanger by thick nitrobenzene feed mouth;
b. stripping tower that is used for removing thick oil of mirbane benzene, the top of stripping tower is provided with a fluid inlet and vapour outlet, the bottom is provided with a steam inlet and liquid outlet, wherein water vapor is entered by steam inlet, the fluid inlet of stripping tower is communicated with the thick oil of mirbane discharge port of tubular heat exchanger by pipeline, take out of with thick oil of mirbane adverse current and with the volatile components benzene in thick oil of mirbane, containing benzene vapour is gone out by vapour outlet, the liquid outlet of stripping tower is communicated with the hot-fluid import of tubular heat exchanger by pipeline, take off oil of mirbane after benzene through tubular heat exchanger to thick oil of mirbane preheating,
C. one is used for except phase separator, this phase separator is provided with fluid inlet, heavy out and light phase export, the fluid inlet of phase separator is communicated with the hot-fluid outlet of tubular heat exchanger by pipeline, the oil of mirbane that takes off after benzene enters phase separator after tubular heat exchanger is to thick oil of mirbane preheating, in oil of mirbane, disperse phase liquid drops in phase separator agglomerate layered and discharges from light phase export and blowdown pipeline;
D. molecular sieve filling tower, the top of this molecular sieve filling tower is provided with fluid inlet, and the bottom is provided with liquid outlet, and fluid inlet is connected with the phase separator heavy out by pipeline, and the oil of mirbane after the phase separator separating-purifying is discharged from the heavy phase outlet, enters the molecular sieve filling tower;
E. product storage tank, the top of this product storage tank is provided with fluid inlet and air outlet, the bottom is provided with liquid outlet, the fluid inlet of product storage tank is connected by the liquid outlet of pipeline with the molecular sieve filling tower, oil of mirbane after molecular sieve filling tower adsorption dewatering is discharged from molecular sieve filling tower liquid outlet, enters product storage tank; Liquid outlet is in order to discharge the oil of mirbane in product storage tank, and the air outlet of product storage tank is used for the nitrogen that displacement produces.
Molecular sieve filling tower of the present invention is two covers, and the fluid inlet of two cover molecular sieve filling towers is connected with the phase separator heavy out by pipeline, and the liquid outlet of two cover molecular sieve filling towers is connected with the fluid inlet of product storage tank by pipeline.
The present invention also comprises a cover molecular sieve filling tower regenerating unit, and is provided with upper and lower inlet mouth in top and the bottom of described molecular sieve filling tower; This molecular sieve filling tower regenerating unit comprises nitrogen pressure compression apparatus and the nitrogen heating unit of serial connection, wherein the inlet mouth of nitrogen pressure compression apparatus connects nitrogen, the air outlet of nitrogen heating unit is connected by the upper and lower inlet mouth of pipeline with molecular sieve filling top of tower and bottom, the nitrogen heating unit is filled with the molecular sieve filling tower with the nitrogen of specified temp and pressure, displaces the moisture in molecular sieve filling.
the present invention also comprises a cover nitrogen gas recovering apparatus, and be provided with the air outlet at the top of described molecular sieve filling tower, described nitrogen gas recovering apparatus comprises a heat exchanger and a nitrogen de-watering apparatus, wherein the entrance of heat exchanger is connected by the air outlet of pipeline with the molecular sieve filling top of tower, the outlet of heat exchanger is connected by the inlet mouth of pipeline with the nitrogen de-watering apparatus, cooling and the rear reuse that dewaters of the nitrogen that molecular sieve filling tower regeneration is used, wherein cooled nitrogen is sent by the air outlet of nitrogen de-watering apparatus, water is discharged by the leakage fluid dram of nitrogen de-watering apparatus, the leakage fluid dram of nitrogen de-watering apparatus is connected with the fluid inlet of phase separator by pipeline.
The invention has the beneficial effects as follows: the one, this process for purification has advantages of operational safety, stripping tower adopts water vapour stripping mode, without the generation of inflammable and explosive substances by product, without hidden peril of explosion; The water that phase separator is removed disperse phase in oil of mirbane belongs to static separation, and operational condition is gentle; Minor amount of water in molecular sieve filling tower Adsorption of Nitrobenzene from Aqueous Solution, service temperature 40-45 ℃, working pressure is lower than 0.5Mpa, in its regenerative process, adopt the high temperature drying nitrogen purging, that suppresses oxygen enters the molecular sieve filling tower, thereby suppress the generation of explosion hazard, and conventional rectification is made with extra care and is operated under the negative pressure hot conditions, produces multiple inflammable and explosive substances in rectifying, and blast process occurs repeatedly.The 2nd, the present invention has advantages of that separation accuracy is high, through stripping tower, phase separator with after the molecular sieve filling tower separates, can efficiently remove benzene and water in thick oil of mirbane, and concentration can reach more than 99.99%.
Description of drawings
The present invention is further described below in conjunction with the drawings and specific embodiments.
Fig. 1 is the schema of the thick oil of mirbane refining plant of the present invention.
Wherein: 1, stripping tower; 2, fluid inlet; 3, vapour outlet; 4, steam inlet; 5, liquid outlet; 6, phase separator; 7, fluid inlet; 8, heavy out; 9, light phase export; 10, molecular sieve filling tower, 10a, molecular sieve filling tower; 11, fluid inlet, 11a, fluid inlet; 12, enterprising gas port, 12a, enterprising gas port; 13, air outlet, 13a, air outlet; 14, liquid outlet, 14a, liquid outlet; 15, lower inlet mouth, 15a, lower inlet mouth; 16, product storage tank; 17, fluid inlet; 18, air outlet; 19, liquid outlet; 20, compressor; 21, nitrogen heater; 22, tensimeter; 23, thermometer; 24, interchanger; 25, inlet mouth; 26, air outlet; 27, entrance of cooling water; 28, cooling water outlet; 29, mist eliminator; 30, air outlet; 31, inlet mouth; 32, leakage fluid dram; 33, blowdown pipeline; 34, bypass.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with concrete example, further set forth the present invention.
Referring to Fig. 1, a kind of for thick oil of mirbane process for purification in the oil of mirbane Chemical Manufacture, it is completed by following steps: (a) at first thick oil of mirbane enter stripping tower 1 after tubular heat exchanger 33 preheatings, volatile component benzene is discharged from the tower top of stripping tower 1 with water vapor, and the oil of mirbane that takes off after benzene enters phase separator 6 at the bottom of the tower of stripping tower 1; (b) oil of mirbane that takes off after benzene is purified in phase separator 6 again, and the water of dispersed enters blowdown pipeline 33 carry out flocking settling in phase separator 6 after, and the oil of mirbane of heavy phase product 99.5% enters molecular sieve filling tower 10; (c) micro-moisture in molecular sieve filling tower 10 selective adsorption nitrobenzene solutions, the oil of mirbane purity after absorption are completed the refining of thick oil of mirbane at this more than 99.99%; (d) oil of mirbane after refining enters product storage tank 16, is used for storing the product after refining.
Thick oil of mirbane refining plant shown in Figure 1, the tubular heat exchanger 33 that is used for the thick oil of mirbane of preheating is provided with thick nitrobenzene feed mouth 34, thick oil of mirbane discharge port 35, hot-fluid import 36, hot-fluid outlet 37; Top for the stripping tower 1 of removing thick oil of mirbane benzene is provided with a fluid inlet 2 and vapour outlet 3, the bottom is provided with a steam inlet 4 and liquid outlet 5, the hot-fluid import 36 of tubular heat exchanger 33 is connected with the liquid outlet 5 of stripping tower 1 bottom by pipeline, and the thick oil of mirbane discharge port 35 of tubular heat exchanger 33 is connected with the fluid inlet 2 at stripping tower 1 top by pipeline.thick oil of mirbane is entered in tubular heat exchanger 33 by the thick nitrobenzene feed mouth 34 of tubular heat exchanger 33, with hot-fluid import 36 by tubular heat exchanger 33 enter take off oil of mirbane heat exchange after benzene after, thick oil of mirbane discharge port 35 by tubular heat exchanger 33, the fluid inlet 2 at stripping tower 1 top enters in stripping tower 1, clean water steam enters stripping tower 1 by the steam inlet 4 of stripping tower 1 bottom, take out of with thick oil of mirbane adverse current and with the volatile components benzene in thick oil of mirbane, containing benzene water vapour is sent by the vapour outlet 3 at stripping tower 1 top, take off oil of mirbane after benzene by the liquid outlet 5 of stripping tower 1 bottom, the hot-fluid import 36 of tubular heat exchanger 33 enters tubular heat exchanger 33 and carries out heat exchange with thick oil of mirbane, the oil of mirbane that takes off after benzene after heat exchange enters phase separator 6 by the liquid outlet 5 of stripping tower 1 bottom.
Phase separator 6 is provided with fluid inlet 7, heavy out 8 and light phase export 9, the disperse phase liquid of taking off in oil of mirbane after benzene that is entered phase separator by fluid inlet 7 drops in phase separator 6 agglomerate layered and discharges from light phase export 9 and blowdown pipeline 33, oil of mirbane after separating-purifying is discharged from heavy phase outlet 8, enters two cover molecular sieve filling towers 10,10a by pipeline.
two cover molecular sieve filling towers 10, 10a can alternate run, two cover molecular sieve filling towers 10, 10a is provided with respectively fluid inlet 11 at the top, 11a, inlet mouth 12, 12a and air outlet 13, 13a, the bottom is provided with liquid outlet 14, 14a and inlet mouth 15, 15a, fluid inlet 11, 11a is connected with the heavy out 8 of phase separator 6 by pipeline, oil of mirbane after adsorption dewatering is from liquid outlet 14, 14a discharges, enter product storage tank 16 by pipeline by the fluid inlet 17 at product storage tank 16 tops, air outlet 18 is used for the nitrogen that displacement produces, liquid outlet 19 is in order to discharge the oil of mirbane in product storage tank 16.molecular sieve filling tower regenerating unit comprises nitrogen pressure compression apparatus and nitrogen heating unit, wherein the nitrogen pressure compression apparatus is a compressor 21, in order to compressed nitrogen the retrieving arrangement nitrogen that refluxes and the fresh nitrogen that replenishes, the nitrogen heating unit is a nitrogen heater 21, the air outlet of compressor 21 is connected with the inlet mouth of nitrogen heater 21, the air outlet of nitrogen heater 21 is by pipeline and two cover molecular sieve filling towers 10, the enterprising gas port 13 on 10a top, the lower inlet mouth 15 of 13a and bottom, 15a is connected, molecular sieve filling tower regenerating unit just can be filled with the nitrogen of specified temp and pressure molecular sieve filling tower 10 like this, 10a, displace the moisture in molecular sieve filling.
Be provided with bypass 34 on nitrogen heater 21, can control whether enable nitrogen heater 21 by valve; Be respectively equipped with tensimeter 22 on the import and export pipeline of compressor 21, also be provided with thermometer 23 on the outlet line of the inlet line of compressor 21 and nitrogen heater 21.When a cover molecular sieve filling tower absorption when saturated, start another set of molecular sieve filling tower, start simultaneously compressor 20 and nitrogen heater 21 is regenerated, dry heat nitrogen enters from lower inlet mouth 15 or the 15a of molecular sieve filling tower 10 or 10a, after setting stripping time; Then close nitrogen heater 21, be blown into normal temperature nitrogen from molecular sieve filling tower 10 or 10a top inlet mouth 12 or 12a simultaneously, molecular sieve filling tower 10 is carried out cooling, after setting cooling time, the regeneration of molecular sieve cooling tower is completed.
Nitrogen gas recovering apparatus comprises a heat exchanger and a nitrogen de-watering apparatus, wherein heat exchanger is an interchanger 24, this interchanger 24 is provided with inlet mouth 25, air outlet 26, entrance of cooling water 27 and cooling water outlet 28, the nitrogen de-watering apparatus is a mist eliminator 29, and this mist eliminator 29 is provided with inlet mouth 31, air outlet 30 and liquid outlet 32.The inlet mouth 25 of interchanger 24 is connected with two cover molecular sieve filling towers 10, the air outlet 13 of 10a, 13a by pipeline, and the air outlet 26 of interchanger 24 is connected with the inlet mouth 31 of mist eliminator 29 by pipeline; The air outlet 30 of mist eliminator 29 is connected with the inlet mouth of compressor 20 in molecular sieve filling tower regenerating unit by pipeline, the liquid outlet 32 of mist eliminator 29 is connected with the fluid inlet 7 of phase separator 6 by pipeline, water coolant is advanced by entrance of cooling water 27, and cooling water outlet 28 goes out.All be provided with thermometer 23 on the air outlet pipeline of the inlet mouth pipeline of interchanger 24 and mist eliminator 29; Be provided with successively respectively tensimeter and thermometer 22,23 on the entrance of cooling water pipeline of interchanger 24 and cooling water outlet pipeline.Nitrogen gas recovering apparatus can molecular sieve filling tower regeneration is used cooling the and rear reuse that dewaters of nitrogen.
Nitrogen gas recovering apparatus and nitrogen heater 21 chain promoters, when nitrogen heater 21 started, nitrogen gas recovering apparatus started simultaneously; When nitrogen heater 21 was closed, nitrogen gas recovering apparatus also was in the operation state for the treatment of.During cooling end, closure molecule sieve packing tower 10, the enterprising gas port 12 of 10a, 12a, lower inlet mouth 15,15a, venting port 13,13a and liquid outlet 14,14a make nitrogen be full of molecular sieve filling tower 10,10a, suppress oxygen and enter, and guarantee parking safety.
Claims (5)
1. a thick oil of mirbane process for purification, is characterized in that, comprises the following steps:
(a) at first thick oil of mirbane enter stripping tower after the tubular heat exchanger preheating, and volatile component benzene is discharged from the tower top of stripping tower with water vapor, and the oil of mirbane that takes off after benzene enters phase separator at the bottom of the tower of stripping tower;
(b) oil of mirbane that takes off after benzene is purified in phase separator again, and the water of dispersed enters blowdown pipeline carry out flocking settling in phase separator after, and the oil of mirbane of heavy phase product 99.5% enters the molecular sieve filling tower;
(c) micro-moisture in molecular sieve filling tower selective adsorption nitrobenzene solution, the oil of mirbane purity after absorption are completed the refining of thick oil of mirbane at this more than 99.99%;
(d) oil of mirbane after refining enters product storage tank and stores.
2. a thick oil of mirbane refining plant, is characterized in that, comprising:
A. a tubular heat exchanger that is used for the thick oil of mirbane of preheating, be provided with thick nitrobenzene feed mouth, thick oil of mirbane discharge port, hot-fluid import, hot-fluid outlet; Wherein thick oil of mirbane is entered in tubular heat exchanger by thick nitrobenzene feed mouth;
b. stripping tower that is used for removing thick oil of mirbane benzene, the top of stripping tower is provided with a fluid inlet and vapour outlet, the bottom is provided with a steam inlet and liquid outlet, wherein water vapor is entered by steam inlet, the fluid inlet of stripping tower is communicated with the thick oil of mirbane discharge port of tubular heat exchanger by pipeline, take out of with thick oil of mirbane adverse current and with the volatile components benzene in thick oil of mirbane, containing benzene vapour is gone out by vapour outlet, the liquid outlet of stripping tower is communicated with the hot-fluid import of tubular heat exchanger by pipeline, take off oil of mirbane after benzene through tubular heat exchanger to thick oil of mirbane preheating,
C. phase separator, this phase separator is provided with fluid inlet, heavy out and light phase export, the fluid inlet of phase separator is communicated with the hot-fluid outlet of tubular heat exchanger by pipeline, the oil of mirbane that takes off after benzene enters phase separator after tubular heat exchanger is to thick oil of mirbane preheating, in oil of mirbane, disperse phase liquid drops in phase separator agglomerate layered and discharges from light phase export and blowdown pipeline;
D. molecular sieve filling tower, the top of this molecular sieve filling tower is provided with fluid inlet, and the bottom is provided with liquid outlet, and fluid inlet is connected with the phase separator heavy out by pipeline, oil of mirbane after the phase separator separating-purifying is discharged from the heavy phase outlet, enters the molecular sieve filling tower;
E. product storage tank, the top of this product storage tank is provided with fluid inlet and air outlet, the bottom is provided with liquid outlet, the fluid inlet of product storage tank is connected by the liquid outlet of pipeline with the molecular sieve filling tower, oil of mirbane after molecular sieve filling tower adsorption dewatering is discharged from molecular sieve filling tower liquid outlet, enters product storage tank; Liquid outlet is in order to discharge the oil of mirbane in product storage tank, and the air outlet of product storage tank is used for the nitrogen that displacement produces.
3. thick oil of mirbane refining plant as claimed in claim 2, it is characterized in that, described molecular sieve filling tower is two covers, the fluid inlet of two cover molecular sieve filling towers is connected with the phase separator heavy out by pipeline, and the liquid outlet of two cover molecular sieve filling towers is connected with the fluid inlet of product storage tank by pipeline.
4. thick oil of mirbane refining plant as claimed in claim 2 or claim 3, is characterized in that, also comprises a cover molecular sieve filling tower regenerating unit, and be provided with upper and lower inlet mouth in top and the bottom of described molecular sieve filling tower; This molecular sieve filling tower regenerating unit comprises nitrogen pressure compression apparatus and the nitrogen heating unit of serial connection, wherein the inlet mouth of nitrogen pressure compression apparatus connects nitrogen, the air outlet of nitrogen heating unit is connected by the upper and lower inlet mouth of pipeline with molecular sieve filling top of tower and bottom, the nitrogen heating unit is filled with the molecular sieve filling tower with the nitrogen of specified temp and pressure, displaces the moisture in molecular sieve filling.
5. thick oil of mirbane refining plant as claimed in claim 4, it is characterized in that, also comprise a cover nitrogen gas recovering apparatus, and be provided with the air outlet at the top of described molecular sieve filling tower, described nitrogen gas recovering apparatus comprises a heat exchanger and a nitrogen de-watering apparatus, wherein the entrance of heat exchanger is connected by the air outlet of pipeline with the molecular sieve filling top of tower, the outlet of heat exchanger is connected by the inlet mouth of pipeline with the nitrogen de-watering apparatus, cooling and the rear reuse that dewaters of the nitrogen that molecular sieve filling tower regeneration is used, wherein cooled nitrogen is sent by the air outlet of nitrogen de-watering apparatus, water is discharged by the leakage fluid dram of nitrogen de-watering apparatus, the leakage fluid dram of nitrogen de-watering apparatus is connected with the fluid inlet of phase separator by pipeline.
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| CN 200910195530 CN102020567B (en) | 2009-09-11 | 2009-09-11 | Method and device for refining coarse nitrobenzene |
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| CN 200910195530 CN102020567B (en) | 2009-09-11 | 2009-09-11 | Method and device for refining coarse nitrobenzene |
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| CN102020567B true CN102020567B (en) | 2013-11-06 |
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Families Citing this family (3)
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| CN108997124B (en) * | 2017-06-06 | 2020-11-10 | 中国石油化工股份有限公司 | Method for recovering nitrobenzene from nitrobenzene tar |
| CN110170185B (en) * | 2019-05-30 | 2023-07-25 | 湖北东方化工有限公司 | Device and method for separating waste sulfuric acid nitro compounds |
| CN115193366B (en) * | 2021-04-09 | 2024-04-09 | 万华化学集团股份有限公司 | Nitration reaction device and method for carrying out nitration reaction by using same |
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Address after: 201201 Shanghai, Pudong New Area Jin Tang Road, No. 2, block B, 145 Patentee after: SHANGHAI ANHORN ENVIRONMENTAL TECHNOLOGY CO., LTD. Address before: 201201 Shanghai, Pudong New Area Jin Tang Road, No. 2, block B, 145 Patentee before: Shanghai Anhorn Mechanical Equipment Co., Ltd. |
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Effective date of registration: 20200313 Address after: 238200 Guangna standardized workshop 9 and 10, zhengpugang New District, Ma'anshan City, Anhui Province Co-patentee after: SHANGHAI ANHORN ENVIRONMENTAL TECHNOLOGY Co.,Ltd. Patentee after: Anhui Annie Environmental Protection Technology Co., Ltd. Address before: 201201 B block, 145 Jin Tang Road, 2, Shanghai, Pudong New Area Patentee before: SHANGHAI ANHORN ENVIRONMENTAL TECHNOLOGY Co.,Ltd. |
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