CN115124212A - Method for treating high-sulfur high-asphaltene oil sludge - Google Patents
Method for treating high-sulfur high-asphaltene oil sludge Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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Abstract
The invention discloses a method for treating high-sulfur high-asphaltene oil sludge. The method comprises the steps of pretreating the high-sulfur high-asphaltene oil sludge before dehydrating and drying the high-sulfur high-asphaltene oil sludge, wherein the pretreatment comprises air catalytic oxidation desulfurization, acidification catalytic modification, neutralization conditioning and standing separation. The pretreated concentrated sludge is subsequently subjected to centrifugal dehydration and low-temperature drying to be used as high-calorific-value fuel and is sent to a hazardous waste incineration unit for treatment, so that the generation of hydrogen sulfide in a treatment system and the adverse effect of asphaltene oil sludge on low-temperature drying are fundamentally avoided, and the calorific value of the dried sludge is improved.
Description
Technical Field
The invention relates to a method for treating high-sulfur high-asphaltene oil sludge, in particular to a method for recycling and reducing high-sulfur high-asphaltene oil sludge, and belongs to the technical field of oil sludge treatment in the petrochemical industry.
Background
In recent years, refinery enterprises adopt high-temperature drying technologies, such as thermal desorption and high-temperature steam injection technologies, for oil sludge treatment, but the problems of high energy consumption, large on-site foul smell and high investment and operating cost exist. The treatment technology of acidifying demulsification and then drying at low temperature is also adopted, and the technology can treat activated sludge, floating slag and oil sludge at the bottom of a light oil tank area, but has the following problems when treating high-sulfur and high-asphaltene oil sludge such as heavy oil sludge and the like: 1. the pretreatment process is long, and pipelines are easy to block; 2. the oil sludge contains malodorous sulfides, and a large amount of hydrogen sulfide gas can be generated after acid is added; 3. the sludge viscosity is high, the pH meter measurement is inaccurate, and the long-period operation cannot be realized. 4. The problem of solidification and blockage exists in the discharging and cooling process of the dried sludge containing high asphaltene. Therefore, the method for low-temperature drying treatment of the high-sulfur high-asphaltene oil sludge is obtained, and has important significance in simple operation, stable operation, reliable effect and low operation cost.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for treating high-sulfur high-asphaltene oil sludge.
Specifically, the invention adopts the following technical means:
the invention provides a pretreatment method for treating high-sulfur high-asphaltene oil sludge, which is to carry out pretreatment on the oil sludge before carrying out dehydration and drying treatment on the oil sludge, wherein the pretreatment comprises the following steps:
(1) adding an oil sludge modification catalyst into the oil sludge, aerating, and performing air catalytic oxidation desulfurization on sulfide in the oil sludge under the action of the oil sludge modification catalyst;
(2) after the reaction is finished, adding concentrated sulfuric acid into the oil sludge obtained in the step (1), carrying out acidification catalytic modification on the oil sludge, and continuing aeration;
(3) after the reaction is finished, adding a sodium hydroxide solution into the oil sludge obtained in the step (2), neutralizing and conditioning the oil sludge, and continuing aeration;
(4) stopping aeration, standing and clarifying the oil sludge obtained in the step (3), and conveying the concentrated sludge to downstream for dehydration and drying treatment.
Preferably, the sludge upgrading catalyst in step (1) is an iron-containing catalyst, and the iron-containing catalyst refers to any catalyst capable of producing Fe 2+ Or Fe 3+ The dosage of the oil sludge modifying catalyst is 20-50 mg of iron ion concentration in each liter of oil sludge.
Preferably, concentrated sulfuric acid is added in the step (2) until the pH of the oil sludge is 0.5-2.0, and a sodium hydroxide solution is added in the step (3) until the pH of the oil sludge is 6-7.5.
Preferably, the oil sludge is stirred by aeration in the step (1), the step (2) and the step (3) to rapidly and uniformly mix the oil sludge and other substances, and the aeration intensity is 9-12 Nm 3 /m 2 . h。
Preferably, the initial temperature of the oil sludge in the step (1) is 35-45 ℃.
Preferably, the time of the air catalytic oxidation desulfurization in the step (1) is 3-4 hours.
Preferably, the time for the acidification catalytic modification in the step (2) is 30-50 minutes.
Preferably, the time for neutralization conditioning in the step (3) is 30-50 minutes.
Preferably, the standing and clarifying time in the step (4) is 4 hours.
The invention also provides program-controlled oil sludge pretreatment equipment, which is used for pretreating high-sulfur high-asphaltene oil sludge before dehydration and drying treatment of the oil sludge; the program-controlled oil sludge pretreatment equipment comprises a vertical cylinder, a supernatant collecting assembly at the middle upper part, an aeration assembly at the lower part and a concentrated sludge discharge assembly at the bottom; the supernatant collecting component comprises a supernatant collecting ring pipe and a supernatant outlet, and the supernatant collecting ring pipe is connected with the supernatant outlet after being converged by three straight pipes which form an angle of 120 degrees with each other; the aeration component comprises a compressed air inlet and an aeration ring pipe connected with the compressed air inlet, and a plurality of flow-dispersing air distributors are arranged on the aeration ring pipe; the concentrated sludge discharge assembly comprises four collecting pipes which are mutually 90 degrees and have open tail ends, and the four collecting pipes are connected with a sludge discharge port after being converged; the program-controlled oil sludge pretreatment equipment is also provided with a sulfuric acid inlet and a sodium hydroxide solution inlet, and concentrated sulfuric acid and a sodium hydroxide solution are introduced into the middle lower part of the program-controlled oil sludge pretreatment equipment through an acid down-lead pipe and an alkali down-lead pipe respectively; the program-controlled oil sludge pretreatment equipment is also provided with an oil sludge inlet, an exhaust port, a first pH monitoring pump inlet, a second pH monitoring pump inlet, a pH monitoring pump return port, a lower flange port of the liquid level meter and an upper flange port of the liquid level meter.
The invention also provides a device for treating high-sulfur high-asphaltene oil sludge, which comprises the program-controlled oil sludge pretreatment equipment, a centrifuge, a dehydrated sludge storage tank, a dryer, a double-shaft cooling screw conveyor and a hazardous waste incineration unit which are sequentially connected through pipelines, wherein the program-controlled oil sludge pretreatment equipment, the dehydrated sludge storage tank and the dryer are respectively connected with an air washing tower through pipelines, the air washing tower is connected with the hazardous waste incineration unit through a pipeline, and the program-controlled oil sludge pretreatment equipment, the centrifuge and the air washing tower are also connected to a sewage treatment plant through pipelines, wherein:
the program-controlled oil sludge pretreatment equipment is used for receiving oil sludge, carrying out air catalytic oxidation desulfurization, acidification catalytic modification, neutralization conditioning, oil-water separation and sludge concentration treatment on the oil sludge, feeding the treated concentrated sludge into the centrifuge, feeding the generated waste gas into the gas washing tower, and feeding the generated sewage into a sewage treatment field;
the centrifugal machine is used for receiving the concentrated sludge from the program-controlled oil sludge pretreatment equipment, adding a flocculating agent to carry out centrifugal dehydration treatment on the concentrated sludge, sending the treated dehydrated sludge into the dehydrated sludge storage tank, and sending the generated sewage to a sewage treatment field;
the dehydrated sludge storage tank is used for receiving and temporarily storing the dehydrated sludge from the centrifugal machine and sending the dehydrated sludge into the dryer, and the generated waste gas is sent into the gas washing tower;
the dryer is used for receiving the dewatered sludge from the dewatered sludge storage tank and drying the dewatered sludge at a low temperature, the dried sludge after treatment is sent to the double-shaft cooling screw conveyor, and the generated waste gas is sent to the gas washing tower;
the double-shaft cooling screw conveyor is used for receiving the dried sludge from the dryer, cooling and conveying the dried sludge, and sending the treated dried sludge to the hazardous waste incineration unit;
the gas washing tower is used for receiving waste gas from the program-controlled oil sludge pretreatment equipment, the dewatered sludge storage tank and the dryer, carrying out gas washing, cooling and pre-purification treatment, sending the treated waste gas into the dangerous waste incineration unit, and sending the generated sewage to a sewage treatment field;
the dangerous waste incineration unit is used for receiving the dried sludge from the double-shaft cooling screw conveyor and the waste gas from the gas washing tower, and incinerating the dried sludge and the waste gas to generate ash which is in cooperation with the ash.
Preferably, a pipeline mixer is arranged at a feed pipeline of the program-controlled oil sludge pretreatment equipment and is connected with a catalyst feeding device.
Preferably, the program-controlled oil sludge pretreatment equipment is connected with an acid adding device, an alkali adding device and a compressed air aeration device.
Preferably, the program-controlled oil sludge pretreatment equipment is provided with a return pipeline, and the return pipeline is provided with a pH monitoring device.
Preferably, the inlet pipeline of the centrifuge is connected with a flocculant feeding device.
Preferably, the heat source of the dryer is connected with a low-pressure steam device.
Preferably, the cavity of the dryer is connected with a nitrogen conveying device.
Preferably, the dryer is a disc dryer, a paddle dryer or an umbrella dryer.
Preferably, the middle upper part of the gas washing tower is provided with a gas washing water spraying device.
The invention also provides a method for treating the high-sulfur high-asphaltene oil sludge, which comprises the following steps:
(1) mixing oil sludge and an oil sludge modification catalyst through a pipeline mixer, then sending the mixture into program-controlled oil sludge pretreatment equipment, starting a compressed air aeration device to aerate the oil sludge, carrying out air catalytic oxidation desulfurization on sulfides in the oil sludge under the action of the oil sludge modification catalyst, automatically stopping conveying the oil sludge and the oil sludge modification catalyst when the liquid level of the program-controlled oil sludge pretreatment equipment reaches a set value, continuing aeration for a set time, and then automatically starting an acid adding device;
(2) keeping aeration, filling concentrated sulfuric acid into the program-controlled oil sludge pretreatment equipment by starting an acid adding device, carrying out acidification and catalytic modification on the oil sludge, automatically starting a pH monitoring device after the running time of the acid adding device reaches a set value, setting the pH value of an outlet of the pH monitoring device, automatically stopping the acid adding device and the pH monitoring device after the pH value reaches the set value, continuously aerating for a set time, and automatically starting an alkali adding device;
(3) keeping aeration, filling a sodium hydroxide solution into the program-controlled oil sludge pretreatment equipment by starting an alkali adding device, neutralizing and conditioning the oil sludge, automatically starting a pH monitoring device after the running time of the alkali adding device reaches a set value, setting the pH value of an outlet of the pH monitoring device, automatically stopping the alkali adding device and the pH monitoring device after the pH value reaches the set value, continuing aeration for the set time, and closing a compressed air aeration device;
(4) standing and clarifying oil sludge in the program-controlled oil sludge pretreatment equipment, opening a supernatant outlet of the program-controlled oil sludge pretreatment equipment, discharging the supernatant to a sewage treatment plant, and sending concentrated sludge at the middle lower part to a centrifuge;
(5) feeding a flocculating agent on a feed pipeline of a centrifuge while conveying the concentrated sludge to the centrifuge, then carrying out centrifugal dehydration treatment on the concentrated sludge by using the centrifuge, conveying the dehydrated sludge to a dehydrated sludge storage tank for temporary storage, and conveying the discharged water of the centrifuge to a sewage treatment plant;
(6) continuously and uniformly feeding the dewatered sludge temporarily stored in the dewatered sludge storage tank into a dryer for low-temperature drying treatment;
(7) cooling and discharging the dried sludge in the dryer by using a double-shaft cooling screw conveyor, and then conveying the dried sludge to a hazardous waste incineration unit for treatment;
(8) in the steps, the waste gas generated in the operation process of the program-controlled oil sludge pretreatment equipment, the dehydrated sludge storage tank and the dryer is sent to the gas washing tower, and the waste gas is washed and purified by the washing gas introduced from the middle upper part of the gas washing tower and then sent to the dangerous waste incineration unit for treatment.
Preferably, the feeding temperature of the oil sludge in the step (1) is 35-45 ℃.
Preferably, the sludge upgrading catalyst in step (1) is an iron-containing catalyst, and the iron-containing catalyst refers to all catalysts capable of producing Fe 2+ Or Fe 3+ The addition amount of the oil sludge modification catalyst is 20-50 mg of iron ion concentration in each liter of oil sludge.
Preferably, the aeration time in the step (1) is 3-4 hours.
Preferably, the pH value set in the step (2) is 0.5-2.0.
Preferably, the aeration time in the step (2) is 30-50 minutes.
Preferably, the pH value set in the step (3) is 6-7.5.
Preferably, in the step (1), the step (2) and the step (3), the oil sludge is stirred so that the oil sludge and other substances are quickly and uniformly mixed.
Preferably, the aeration intensity in the step (1), the step (2) and the step (3) is 9-12 Nm 3 /m 2 . h。
Preferably, the pH monitoring device in the step (2) and the step (3) is arranged on a return pipeline of the program-controlled oil sludge pretreatment equipment, and a filter and a back flushing pipeline are arranged in front of the pump, so that the accuracy of measurement and long-period operation are ensured.
Preferably, the aeration time in the step (3) is 30-50 minutes.
Preferably, the standing and clarifying time in the step (4) is 4 hours.
Preferably, the flocculant in the step (5) is a cationic organic polymer flocculant.
Preferably, in the step (6), the heat source of the dryer adopts low-pressure saturated water vapor with the temperature of 170 ℃ and the pressure of 0.7MPag, the exhaust temperature of the cavity of the dryer is controlled to be 100-115 ℃, the oxygen content in the dryer is 0.8-1.6%, and the dryer operates under micro-negative pressure.
The principle and the beneficial effects of the invention comprise:
1. program-controlled pretreatment of oil sludge
1.1 addition of oil sludge modification catalyst
And adding an oil sludge modification catalyst on a pipeline for the oil sludge to enter the program-controlled oil sludge pretreatment equipment, and uniformly mixing the oil sludge and the oil sludge modification catalyst through a pipeline mixer.
The oil sludge modification catalyst adopted by the invention is an iron-containing catalyst, and the iron-containing catalyst is mainly used as the oil sludge modification catalyst in the pretreatment process of high-sulfur high-asphaltene oil sludge and has the following three functions:
(1) catalyst for desulfurization and deodorization of oil sludge
Under the condition that the pH value is more than or equal to 6.0 and compressed air is blown in, the oil sludge modification catalyst reacts with sulfide in the oil sludge.
If the iron-containing catalyst is Fe 3+ The following reaction occurs:
2Fe 3+ +3S 2- →Fe 2 S 3 [1]
Fe 2 S 3 +6O 2 →2Fe 3+ +3SO 4 2- [2]
if the iron-containing catalyst is Fe 2+ The following reaction occurs:
Fe 2+ +S 2- →FeS [3]
FeS+2O 2 →SO 4 2- +Fe 2+ [4]
while Fe 2+ There is another oxidation route as a catalyst, i.e. first oxidized to Fe 3+ ：
4Fe 2+ +O 2 +2H 2 O→4Fe 3+ +4OH - [5]
Then the reactions of the above [1] and [2] take place.
(2) Catalyst for oleic modification of asphaltene
When the pH is less than or equal to 2.0, Fe 3+ Can promote the solidification and modification of asphaltene oil to generate insolubilityAsphaltene deposits:
asphaltene oil + H + (pH≤2.0)+Fe 3+ (catalyst) → asphaltene ↓ -
(3) Coagulant for sludge conditioning
In the process of adding alkali for neutralization and conditioning, the pH is 6-8, and Fe 3+ A series of inorganic high molecular polymers are generated, coagulation and flocculation are generated on solid particles in the pretreated oil sludge, and the settling and dewatering performance of the oil sludge is improved.
1.2 air catalytic oxidative desulfurization
The compressed air device is started, the oil sludge is aerated and stirred by the aid of the flow dispersing air distributor, the compressed air is cut twice by the tooth-shaped air distribution head and the tooth-shaped flow dispersing cover, the diameter of bubbles is reduced, the gas-liquid contact area is increased, and the utilization rate of oxygen is improved. And (3) carrying out air catalytic oxidation desulfurization treatment on the malodorous sulfides in the oil sludge under the action of an oil sludge modification catalyst.
The method for carrying out air catalytic oxidation desulfurization and acidification catalytic modification on the oil sludge avoids the direct acidification to generate a large amount of hydrogen sulfide gas. Meanwhile, malodorous sulfides in the oil sludge are catalytically oxidized into sulfates by air, so that the aim of deodorizing the oil sludge is fulfilled.
Aeration intensity Q (Nm) required for desulfurization 3 /m 2 H) is calculated as follows:
in the formula: m: sludge treatment amount (m) 3 )；
eta: the utilization rate of oxygen is 30-40%;
ρ: the density of oxygen in the standard state, i.e., 1.428 g/L;
k: the volume fraction of oxygen in air, i.e. 21%;
s: aeration area, the value of which is the bottom area (m) of the program-controlled oil sludge pretreatment equipment 2 )；
t: the aeration time is 3-4 hours (h);
when the liquid level of the program-controlled oil sludge pretreatment equipment reaches a set value, the conveying of the oil sludge and the oil sludge modification catalyst is stopped, and aeration is continued for two hours to ensure that sulfides in the oil sludge are completely oxidized and then the next procedure is carried out.
1.3 acidification catalytic upgrading
And starting an acid adding device, and adding concentrated sulfuric acid into the program-controlled oil sludge pretreatment equipment to carry out acidification, catalysis and modification treatment on the oil sludge.
High asphaltene oil, acidified to pH less than or equal to 2, and in the presence of a suitable amount of Fe 3+ If present, will rapidly upgrade to produce an asphaltene solid deposit. The generation of asphaltene deposits changes the characteristics of asphaltene sludge to make it at low temperature (heat source temperature)<The dried material does not show the characteristics of asphaltene any more during drying at 180 ℃, the problems of adhesion, solidification, blockage, caking and the like of the discharged material in the drying process are avoided, and the dried discharged material does not need to be cut or crushed and can be directly discharged by adopting a double-shaft cooling screw conveyor.
1.4, neutralization Condition
And (4) starting the alkali adding device after the acid adding device is stopped to neutralize and condition the oil sludge.
1.5, discharging supernatant and concentrated sludge
After the acidification modification and neutralization conditioning of the oil sludge are finished, standing and clarifying are carried out, so that the oil sludge is subjected to oil-water separation and sludge concentration and sedimentation, and the supernatant is discharged to a sewage treatment plant for treatment, thereby reducing the load of a centrifuge.
2. Dewatering of concentrated sludge
Concentrated sludge at the lower part of the program-controlled oil sludge pretreatment equipment is conveyed to a centrifuge by a pump, and meanwhile, a cationic organic polymeric flocculant is added on a feed pipe line of the centrifuge to carry out centrifugal dehydration treatment on the concentrated sludge, so that the water content of the sludge is reduced to 70-85%, and conditions are created for low-temperature drying.
3. Dewatered sludge drying
The dewatered sludge is stored in a dewatered sludge storage tank and continuously and uniformly lifted to a dryer by a pump for low-temperature drying treatment, and the water content of the sludge can be reduced to 5-15%. The water content of the dried sludge can be adjusted according to the composition condition of the colloid in the fed heavy oil sludge. When the content of colloid which is not easy to generate dust is high, the water content of discharged materials can be reduced to about 5 percent.
4. Dried sludge conveying and disposal
Because the raw material oil sludge is subjected to modification pretreatment, the dried sludge at the outlet of the dryer does not agglomerate, and therefore, the dried sludge can be directly cooled and discharged through the double-shaft cooling screw conveyor.
The water content of the dried sludge is about 10%, and the heat value is about 3500-5500 kcal/kg, so that the dried sludge can be used as an auxiliary fuel of a hazardous waste incineration treatment facility for heat value utilization and further reduction treatment.
5. System waste gas and waste water treatment
Waste gas generated by the program-controlled oil sludge pretreatment equipment, the dewatered sludge storage tank and the dryer is introduced into the scrubbing tower by using the induced draft fan. And introducing gas washing water into the middle upper part of the gas washing tower to cool and purify the waste gas, and introducing the purified waste gas into the hazardous waste incineration unit. And the drained water of the program-controlled oil sludge pretreatment equipment, the centrifugal machine and the gas washing tower enters a sewage treatment field.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the oil sludge is desulfurized firstly, the malodorous sulfide is converted into sulfate, and then other treatments are carried out, so that the generation of hydrogen sulfide is fundamentally avoided, and the environment is more friendly to human beings.
2. The method ensures that the oil sludge does not have the characteristic of asphaltene under the low-temperature drying condition by carrying out acidification modification pretreatment on the oil sludge, thereby ensuring the continuous operation of the low-temperature drying of the oil sludge.
3. The program-controlled oil sludge pretreatment equipment provided by the invention adopts program control and integrated design, integrates multiple functions of air catalytic oxidation desulfurization, acidification catalytic modification, neutralization conditioning, oil-water separation and sludge concentration of the oil sludge, shortens the process flow, avoids pipeline blockage, and saves investment and land occupation.
4. The invention optimizes the design of pH monitoring. Through the design of the inlet pipeline, one for one, and the purging pipeline of the pH monitoring device, the accuracy of pH measurement and the long-period operation of the pH meter are ensured.
5. The dried sludge obtained by the invention has high heat value, can be used as an auxiliary fuel of a hazardous waste incineration unit, and realizes the maximum reduction treatment.
Drawings
FIG. 1 is a process flow diagram of a high sulfur high asphaltene sludge treatment process according to the invention;
FIG. 2 is a schematic diagram of the connection of a high sulfur high asphaltene sludge treatment plant according to the invention;
FIG. 3 is a schematic diagram of the programmable sludge pretreatment apparatus of the present invention;
FIG. 4 is a schematic diagram of the supernatant collection loop of the programmable sludge pretreatment apparatus of the present invention;
FIG. 5 is a schematic structural diagram of a concentrated sludge discharge assembly of the program-controlled sludge pretreatment apparatus of the present invention;
fig. 6 is a schematic structural diagram of an aeration assembly of the program-controlled sludge pretreatment apparatus of the present invention;
fig. 7 is a schematic diagram of a flow distributor of the present invention.
Description of reference numerals:
1-a vertical cylinder; 2-oil sludge inlet; 3-compressed air inlet; 4-sulfuric acid inlet; 5-sodium hydroxide solution inlet; 6-supernatant discharge port; 7-a sludge discharge port; 8-an exhaust port; 9-a lower flange opening of the liquid level meter; 10-an upper flange opening of the liquid level meter; 11-first pH monitoring pump inlet; 12-a second pH monitoring pump inlet; 13-a pH monitoring pump return port; 14-a collection tube; 15-an aeration ring pipe; 16-a distributed flow air distributor; 17-collecting the supernatant into a ring pipe; 18-acid down-lead; 19-alkali down-leading pipe; 20-water collecting small holes; 21-a central tube; 22-a reinforcement plate; 23-a diffuser; 24-gas distribution head.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
Examples of the experiments
A plurality of heavy crude oil tank areas used for asphalt production by a petrochemical enterprise are taken, and after being uniformly stirred, 600ml of heavy crude oil tank areas are respectively poured into 1000ml of beakers which are marked as samples No. 1, No. 2 and No. 3.
1.6ml of 0.02mol/L ferric sulfate is added into the samples No. 1 and No. 2 respectively to be used as a catalyst for modifying the oil sludge (because the added amount of the ferric sulfate is less, the mass increase caused by the conversion of the ferric sulfate into the ferric hydroxide in the subsequent experiment process can be ignored). Simultaneously, 1.6ml of clear water was added to sample # 3.
The pH of the three samples was adjusted to 1.5 with 10% sulfuric acid and stirring was continued for 10 minutes, and then the pH of the samples was adjusted to 7.0 with 15% sodium hydroxide solution and stirring was continued for 10 minutes and stopped.
The samples 1# and 3# were extracted with petroleum ether as an extractant, and the oil content of the sample 1# was 4.4%, the solids content was 4.7%, and the calorific value of the oven-dried sludge was 5151 kcal/kg. The oil content of the sample No. 3 is 5.3%, the solid content is 3.8%, and the calorific value of the oven-dried sludge is 4465 kcal/kg.
The sample No. 2 was subjected to extraction treatment using benzene as an extractant, and it was found that the oil content of the sample No. 2 was 6.6%, the solid content was 2.5%, and the calorific value of the absolutely dry sludge was 3488 kcal/kg.
The experimental results comparing the 1# and 2# samples show that: the solid material produced by acidification catalytic reforming can be dissolved by benzene.
The experimental results comparing the 1# and 3# samples show that: after the acidification catalysis modification treatment, a part of heavy oil is converted into solid matters, solid components are increased, and the heat value of absolutely dry sludge is improved.
Example 1
A high-sulfur high-asphaltene sludge treatment apparatus and method of the present embodiment are shown in fig. 1 to 2.
The device of this embodiment is including looping through programme-controlled fatlute preprocessing equipment, centrifuge, dehydration mud storage tank, desiccator, biax cooling screw conveyer and the useless unit of burning of danger of pipe connection, just programme-controlled fatlute preprocessing equipment dehydration mud storage tank with the desiccator is connected with the scrubbing tower through the pipeline respectively, the scrubbing tower pass through the pipeline with the useless unit connection that burns of danger, just programme-controlled fatlute preprocessing equipment centrifuge with the scrubbing tower still is through pipe connection to sewage treatment field, wherein:
the program-controlled oil sludge pretreatment equipment receives external oil sludge through an oil sludge lifting pump, and a pipeline mixer is also arranged at a feeding pipeline of the program-controlled oil sludge pretreatment equipment and connected with an oil sludge modification catalyst feeding device; the program-controlled oil sludge pretreatment equipment is also connected with an acid adding device for adding concentrated sulfuric acid, an alkali adding device for adding sodium hydroxide solution and a compressed air aeration device for aeration; the program-controlled oil sludge pretreatment equipment is used for carrying out air catalytic oxidation desulfurization, acidification catalytic modification, neutralization conditioning, oil-water separation and sludge concentration treatment on oil sludge; the treated concentrated sludge is sent into a centrifuge through a centrifuge feeding pump, the generated waste gas is sent into a scrubber tower through a draught fan, and the supernatant is sent to a sewage treatment plant; the program-controlled oil sludge pretreatment equipment is also provided with a return pipeline, and a pH monitoring pump is arranged on the return pipeline;
the specific structure of the program-controlled oil sludge pretreatment equipment is shown in fig. 3 to 7, and the program-controlled oil sludge pretreatment equipment comprises a vertical cylinder 1, a supernatant collecting assembly at the middle upper part, an aeration assembly at the lower part and a concentrated sludge discharge assembly at the bottom; the supernatant collecting component comprises a supernatant collecting ring pipe 17 and a supernatant outlet 6, the supernatant collecting ring pipe 17 is connected with the supernatant outlet 6 after being converged by three straight pipes which form an angle of 120 degrees with each other, a plurality of water collecting small holes 20 are uniformly distributed on the supernatant collecting ring pipe 17, and the openings of the small holes are downward; the aeration component comprises a compressed air inlet 3 and an aeration ring pipe 15 connected with the compressed air inlet, a plurality of flow-dispersing air distributors 16 are arranged on the aeration ring pipe 15, and each flow-dispersing air distributor 16 consists of a central pipe 21, a reinforcing plate 22, a flow-dispersing cover 23 and an air distribution head 24; the concentrated sludge discharge assembly comprises four collecting pipes 17 which are mutually 90 degrees and have open tail ends, and the four collecting pipes are connected with the sludge discharge port 7 after being converged; the program-controlled oil sludge pretreatment equipment is also provided with a sulfuric acid inlet 4 and a sodium hydroxide solution inlet 5, and concentrated sulfuric acid and a sodium hydroxide solution are respectively introduced into the middle lower part of the program-controlled oil sludge pretreatment equipment through an acid down-lead pipe 18 and an alkali down-lead pipe 19; the program-controlled oil sludge pretreatment equipment is also provided with an oil sludge inlet 2, an exhaust port 8, a first pH monitoring pump inlet 11, a second pH monitoring pump inlet 12, a pH monitoring pump return port 13, a lower flange port 9 of a liquid level meter and an upper flange port 10 of the liquid level meter;
the centrifuge receives the concentrated sludge from the program-controlled sludge pretreatment equipment through a centrifuge feed pump, and a pipeline mixer is also arranged at a feed pipeline of the centrifuge and connected with a cationic organic polymeric flocculant feed device; the centrifugal machine is used for carrying out centrifugal dehydration treatment on the concentrated sludge; the treated dehydrated sludge is sent into the dehydrated sludge storage tank, and the discharged sewage is sent to a sewage treatment plant;
the dewatered sludge storage tank receives and temporarily stores the dewatered sludge from the centrifuge, the dewatered sludge is conveyed into the dryer through a dryer feed pump, and the generated waste gas is conveyed into the scrubber tower through the induced draft fan;
the dryer receives dewatered sludge from the dewatered sludge storage tank through a dryer feed pump; a heat source of the dryer is connected with a low-pressure steam device, and a cavity is connected with a nitrogen conveying device; the dryer is a disc dryer; the dryer is used for carrying out low-temperature drying treatment on the dewatered sludge; the treated dried sludge is sent into the double-shaft cooling screw conveyor, and the generated waste gas is sent into a scrubber tower through a draught fan;
the double-shaft cooling screw conveyor is used for receiving the dried sludge from the dryer, cooling the dried sludge and conveying the dried sludge to the hazardous waste incineration unit;
the program-controlled oil sludge pretreatment equipment is connected with the dewatered sludge storage tank through a drying machine, the program-controlled oil sludge pretreatment equipment is connected with the dewatered sludge storage tank through a program-controlled oil sludge storage tank, the program-controlled oil sludge storage tank is connected with the program-controlled oil sludge pretreatment equipment through a program-controlled oil sludge storage tank, the program-controlled oil sludge pretreatment equipment is connected with the program-controlled oil sludge storage tank through a program-controlled oil sludge storage tank, the program-controlled oil sludge storage tank is connected with the program-controlled oil sludge pretreatment equipment through a program-controlled oil sludge storage tank;
the dangerous waste incineration unit is used for receiving the dried sludge from the double-shaft cooling screw conveyor and the waste gas from the gas washing tower, and incinerating the dried sludge and the waste gas to generate ash which is in cooperation with the ash.
The method of the embodiment comprises the following steps:
(1) starting an oil sludge feeding pump and an oil sludge modification catalyst feeding pump simultaneously, mixing oil sludge with the temperature of 35-45 ℃ and the oil sludge modification catalyst through a pipeline mixer, and then feeding the mixture into program-controlled oil sludge pretreatment equipment from an oil sludge inlet, wherein the oil sludge modification catalyst is an iron-containing catalyst, the dosage of the iron-containing catalyst is 20-50 mg of iron ion concentration in each liter of oil sludge, after 10 minutes, a compressed air valve V1 is opened, the oil sludge is stirred and aerated through an aeration component, and the aeration intensity is 9-12 Nm 3 /m 2 . h, carrying out air catalytic oxidation desulfurization on sulfides in the oil sludge under the action of an oil sludge modification catalyst, automatically stopping an oil sludge lifting pump and an oil sludge modification catalyst feeding pump when the liquid level of the program-controlled oil sludge pretreatment equipment reaches a set value (according to specific conditions), continuously aerating for 3-4 hours in the step, completing air catalytic oxidation desulfurization, and automatically starting an acid adding pump;
(2) keeping aeration, filling concentrated sulfuric acid into the program-controlled oil sludge pretreatment equipment through a sulfuric acid inlet and an acid down-leading pipe by starting an acid adding pump, carrying out acidification and catalytic modification on the oil sludge, automatically starting a pH monitoring pump after the operation time of the acid adding pump reaches a set value (according to specific conditions), controlling the pH value of the outlet of the pH monitoring pump to be 0.5-2.0 by using the acid adding pump, automatically stopping the acid adding pump and the pH monitoring pump after the pH value reaches the set value, continuing aeration until the aeration time in the step reaches 30-50 minutes, and automatically starting an alkali adding pump;
(3) keeping aeration, filling a sodium hydroxide solution into the program-controlled oil sludge pretreatment equipment through a sodium hydroxide solution inlet and an alkali down-leading pipe by starting an alkali adding pump, neutralizing and conditioning the oil sludge, automatically starting a pH monitoring pump after the operation time of an alkali adding device reaches a set value (according to specific conditions), controlling the pH value of an outlet of the pH monitoring pump to be 6-7.5 by the alkali adding pump, automatically stopping the alkali adding pump and the pH monitoring pump after the pH value reaches the set value, continuing aeration until the aeration time in the step reaches 30-50 minutes, and closing a compressed air valve V1;
in the step (2) and the step (3), in the operation process of the pH monitoring pump, when the display value of a pump outlet flow meter is lower than 50% of the rated flow of the pump, the pump inlet pipeline is automatically switched; referring to fig. 2, during normal operation, the valve V6 is fully opened, the valve V3, the valve V4 and the valve V5 are all in a closed state, when the outlet flow of the pH monitoring pump is lower than 50% of the rated flow of the pump, the automatic interlock valve V4 is opened, the valve V6 is closed, and the valve V5 is opened, that is, the blocked pipeline and the filter are purged while the standby pipeline is opened;
(4) standing and clarifying the oil sludge in the program-controlled oil sludge pretreatment equipment, opening a valve V2 after 4 hours, collecting and discharging supernatant to a sewage treatment field by a supernatant collection assembly, automatically closing a valve V2 when a liquid level meter reaches a set value, starting a centrifuge feeding pump, and conveying the concentrated sludge at the middle lower part of the program-controlled oil sludge pretreatment equipment to a centrifuge by a concentrated sludge discharge assembly;
(5) feeding a cationic organic polymer flocculant on a feed pipeline of a centrifugal machine while conveying the concentrated sludge to the centrifugal machine, then carrying out centrifugal dehydration treatment on the concentrated sludge by using the centrifugal machine, conveying the dehydrated sludge to a dehydrated sludge storage tank for temporary storage, and conveying the discharged water of the centrifugal machine to a sewage treatment plant;
(6) continuously and uniformly lifting the dewatered sludge temporarily stored in the dewatered sludge storage tank to a dryer by a pump for low-temperature drying treatment, wherein the heat source of the dryer adopts low-pressure saturated water vapor with the temperature of 170 ℃ and the pressure of 0.7MPag, the temperature of a cavity of the dryer is controlled to be 100-115 ℃, an oxygen content analyzer is arranged on an exhaust pipeline of the dryer, nitrogen is introduced into the cavity of the dryer, the oxygen content of exhaust gas is controlled to be 0.8-1.6%, and the dryer operates under micro-negative pressure;
(7) cooling and discharging the dried sludge in the dryer by using a double-shaft cooling screw conveyor, and then conveying the dried sludge to a hazardous waste incineration unit for treatment;
(8) in the steps, the waste gas generated in the operation process of the program-controlled oil sludge pretreatment equipment, the dewatered sludge storage tank and the dryer is sent to the scrubber tower through the induced draft fan, the waste gas is washed and purified by the scrubber gas introduced from the middle upper part of the scrubber tower, and then the waste gas is sent to the hazardous waste incineration unit through the induced draft fan for treatment.
Example 2
7000kg of oil sludge is generated by a certain petrochemical enterprise every day, and the solid content of the oil sludge is measured to be 2.0%, the oil content of the oil sludge is measured to be 7.25%, and the sulfide concentration of the oil sludge is 318 mg/L. Using a sludge lift pump (screw pump, flow 7 m) 3 H, 20m lift) the sludge was lifted to a program controlled sludge pre-treatment facility and treated using the high sulfur high asphaltene sludge treatment apparatus and method of example 1.
The program-controlled oil sludge pretreatment equipment is made of glass fiber reinforced plastic, the diameter is 1.3 meters, the height is 8 meters, and the designed effective water depth is 6.5 meters. The flow of an oil sludge modification catalyst feed pump is 60L/h, the catalyst adopts a ferric sulfate solution with the concentration of 1%, the oil sludge lifting pump and the oil sludge modification catalyst feed pump are interlocked and started simultaneously, and the catalyst is added according to the iron ion concentration of 24 mg/L; starting compressed air to perform catalytic oxidation desulfurization on the oil sludge, wherein the aeration intensity of the compressed air is 9Nm 3 /m 2 H, when the liquid level measured by the double-flange liquid level meter reaches 6.5 meters, automatically stopping the oil sludge lifting pump and the oil sludge modification catalyst feeding pump, continuing aeration and stirring until the air catalytic oxidation desulfurization time reaches 4 hours, taking 500mL of oil sludge sample to measure sulfides in the oil sludge sample, and measuring the concentration of the sulfides to be 0.73 mg/L;
the acid adding pump (metering pump, flow 200L/h, lift 40m) is automatically started, and the pH monitoring pump (pneumatic diaphragm pump, flow 2 m) is started after 10 minutes 3 And h), when the measured value of the pH meter reaches 1.5, automatically stopping the acid adding pump and the pH monitoring pump, continuing aeration and stirring until the acidification, catalysis and modification time reaches 40 minutes, automatically starting the alkali adding pump (a metering pump, the flow rate is 500l/h, the head is 30m), and starting the pH monitoring pump after 10 minutes. When the pH value is measured to reach 6.8, the alkali pump and the pH monitoring pump are stopped to continue aeration, and the solid content of the oil sludge is measured to be 3.81% by sampling in the aeration process; the compressed air inlet valve is automatically closed after the aeration and stirring are continued until the neutralization conditioning time reaches 40 minutesStanding and concentrating the oil sludge; opening a supernatant discharge valve after 4 hours, discharging the supernatant to a sewage treatment system, and discharging about 1000kg of the supernatant;
after the supernatant is discharged, opening a compressed air inlet valve, uniformly stirring the concentrated sludge, and then sampling to obtain a concentrated sludge solid content of 4.44% at the bottom of the program-controlled oil sludge pretreatment equipment; the inlet valve of the compressed air is closed, and the centrifuge feed pump (screw pump, flow 6 m) is started 3 H, the head is 30m) to send the concentrated sludge to a centrifugal dehydrator; measuring the water content of the dewatered sludge to be 81 percent after centrifugal dewatering; the program-controlled oil sludge pretreatment equipment and the centrifuge complete two batches of oil sludge treatment every day; temporarily storing the dewatered sludge in 6m 3 The dewatered sludge storage tank;
continuously and uniformly lifting the dewatered sludge into a dryer by using a dryer feed pump (screw pump, flow rate of 120kg/h), wherein the dryer adopts a hollow blade dryer with the area of 12m 2 The heat source was 0.7MPag of saturated water vapor. Discharging the dried sludge through a double-shaft cooling screw conveyor; obtaining 578kg of dried sludge on average every day, wherein the water content of the dried sludge is 7.97 percent and the heat value is 4968 kcal/kg;
the determination process of the inorganic solid content comprises the following steps: after 2g of the dried sludge was placed in a muffle furnace at 600 ℃ for 2 hours, the weight was 0.187g, giving the actual inorganic solids content after drying: 0.187g/2g 100% ═ 9.35%.
Claims (10)
1. The pretreatment method for the high-sulfur high-asphaltene oil sludge is characterized in that the oil sludge is pretreated before being subjected to dehydration and drying treatment, and the pretreatment comprises the following steps:
(1) adding an oil sludge modification catalyst into the oil sludge, aerating, and performing air catalytic oxidation desulfurization on sulfides in the oil sludge under the action of the oil sludge modification catalyst;
(2) after the reaction is finished, adding concentrated sulfuric acid into the oil sludge obtained in the step (1), carrying out acidification catalytic modification on the oil sludge, and continuing aeration;
(3) after the reaction is finished, adding a sodium hydroxide solution into the oil sludge obtained in the step (2), neutralizing and conditioning the oil sludge, and continuing aeration;
(4) stopping aeration, standing and clarifying the oil sludge obtained in the step (3), and conveying the concentrated sludge to downstream for dehydration and drying treatment.
2. The pretreatment method according to claim 1, wherein the sludge upgrading catalyst in the step (1) is an iron-containing catalyst, and the iron-containing catalyst refers to all catalysts capable of producing Fe 2+ Or Fe 3+ The addition amount of the oil sludge modification catalyst is 20-50 mg of iron ion concentration in each liter of oil sludge.
3. The pretreatment method according to claim 1, wherein concentrated sulfuric acid is added in the step (2) until the pH of the sludge is 0.5 to 2.0, and a sodium hydroxide solution is added in the step (3) until the pH of the sludge is 6 to 7.5.
4. The pretreatment method according to claim 1, wherein the oil sludge is stirred by aeration in the step (1), the step (2) and the step (3) to rapidly and uniformly mix the oil sludge and other substances, and the aeration intensity is 9-12 Nm 3 /m 2 . h。
5. The pretreatment method according to claim 1, wherein:
the initial temperature of the oil sludge in the step (1) is 35-45 ℃;
the time for air catalytic oxidation desulfurization in the step (1) is 3-4 hours;
the time for acidifying, catalyzing and modifying in the step (2) is 30-50 minutes;
the time for neutralization conditioning in the step (3) is 30-50 minutes;
the standing and clarifying time in the step (4) is 4 hours.
6. A method for treating high-sulfur high-asphaltene oil sludge is characterized by comprising the following steps:
(1) mixing oil sludge and an oil sludge modifying catalyst through a pipeline mixer, then sending the mixture into program-controlled oil sludge pretreatment equipment, starting a compressed air aeration device to aerate the oil sludge, carrying out air catalytic oxidation desulfurization on sulfides in the oil sludge under the action of the oil sludge modifying catalyst, automatically stopping conveying the oil sludge and the oil sludge modifying catalyst when the liquid level of the program-controlled oil sludge pretreatment equipment reaches a set value, continuing aeration for a set time, and then automatically starting an acid adding device;
(2) keeping aeration, filling concentrated sulfuric acid into the program-controlled oil sludge pretreatment equipment by starting an acid adding device, carrying out acidification and catalytic modification on the oil sludge, automatically starting a pH monitoring device after the running time of the acid adding device reaches a set value, setting the pH value of an outlet of the pH monitoring device, automatically stopping the acid adding device and the pH monitoring device after the pH value reaches the set value, continuously aerating for a set time, and automatically starting an alkali adding device;
(3) keeping aeration, filling a sodium hydroxide solution into the program-controlled oil sludge pretreatment equipment by starting an alkali adding device, neutralizing and conditioning the oil sludge, automatically starting a pH monitoring device after the running time of the alkali adding device reaches a set value, setting the pH value of an outlet of the pH monitoring device, automatically stopping the alkali adding device and the pH monitoring device after the pH value reaches the set value, continuing aeration for the set time, and closing a compressed air aeration device;
(4) standing and clarifying oil sludge in the program-controlled oil sludge pretreatment equipment, opening a supernatant outlet of the program-controlled oil sludge pretreatment equipment, discharging the supernatant to a sewage treatment plant, and sending concentrated sludge at the middle lower part to a centrifuge;
(5) feeding a flocculating agent on a feed pipeline of a centrifugal machine while conveying the concentrated sludge to the centrifugal machine, then carrying out centrifugal dehydration treatment on the concentrated sludge by using the centrifugal machine, conveying the dehydrated sludge to a dehydrated sludge storage tank for temporary storage, and conveying the drainage of the centrifugal machine to a sewage treatment plant;
(6) continuously and uniformly feeding the dewatered sludge temporarily stored in the dewatered sludge storage tank into a dryer for low-temperature drying treatment;
(7) cooling and discharging the dried sludge in the dryer by using a double-shaft cooling screw conveyor, and then conveying the dried sludge to a hazardous waste incineration unit for treatment;
(8) in the steps, the waste gas generated in the operation process of the program-controlled oil sludge pretreatment equipment, the dehydrated sludge storage tank and the dryer is sent to the gas washing tower, and the waste gas is washed and purified by the washing gas introduced from the middle upper part of the gas washing tower and then sent to the dangerous waste incineration unit for treatment.
7. The process of claim 6, wherein the sludge upgrading catalyst in step (1) is an iron-containing catalyst, the iron-containing catalyst being any catalyst capable of producing Fe 2+ Or Fe 3+ The addition amount of the oil sludge modification catalyst is 20-50 mg of iron ion concentration in each liter of oil sludge.
8. The method according to claim 6, wherein the pH set value in the step (2) is 0.5 to 2.0, and the pH set value in the step (3) is 6 to 7.5.
9. The method according to claim 6, wherein the oil sludge is stirred by aeration in the step (1), the step (2) and the step (3) so that the oil sludge and other substances are quickly and uniformly mixed, and the aeration intensity is 9-12 Nm 3 /m 2 . h。
10. The method of claim 6, wherein:
the feeding temperature of the oil sludge in the step (1) is 35-45 ℃;
the aeration time in the step (1) is 3-4 hours;
the aeration time in the step (2) is 30-50 minutes;
the aeration time in the step (3) is 30-50 minutes;
the pH monitoring device in the step (2) and the step (3) is arranged on a return pipeline of the program-controlled oil sludge pretreatment equipment, and a filter and a back flushing pipeline are arranged in front of a pump, so that the accuracy of measurement and long-period operation are ensured;
standing and clarifying for 4 hours in the step (4);
the flocculant in the step (5) is a cationic organic polymer flocculant;
in the step (6), the heat source of the dryer adopts low-pressure saturated water vapor with the temperature of 170 ℃ and the pressure of 0.7MPag, the exhaust temperature of the cavity of the dryer is controlled to be 100-115 ℃, the oxygen content in the dryer is 0.8-1.6%, and the dryer operates under the micro-negative pressure.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58171473A (en) * | 1982-04-02 | 1983-10-08 | Nippon Oil Co Ltd | Solvent deasphalting of asphaltene-containing hydrocarbon |
| CN1579956A (en) * | 2003-08-08 | 2005-02-16 | 罗德春 | Method for treating high-sulphur-phenol waste alkali liquor under normal temperature and pressure conditions |
| CN101492231A (en) * | 2008-05-28 | 2009-07-29 | 罗德春 | Method for innocent treatment of bottom oil sludge, scruff and active sludge in petro-chemical industry |
| JP2012076047A (en) * | 2010-10-05 | 2012-04-19 | Taiheiyo Cement Corp | Sewage sludge treating method |
| CN111925085A (en) * | 2020-08-25 | 2020-11-13 | 西安德兴环保科技有限公司 | Oil sludge treatment method suitable for heavy bottom oil sludge and tank cleaning oil sludge |
-
2022
- 2022-06-24 CN CN202210730798.XA patent/CN115124212B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58171473A (en) * | 1982-04-02 | 1983-10-08 | Nippon Oil Co Ltd | Solvent deasphalting of asphaltene-containing hydrocarbon |
| CN1579956A (en) * | 2003-08-08 | 2005-02-16 | 罗德春 | Method for treating high-sulphur-phenol waste alkali liquor under normal temperature and pressure conditions |
| CN101492231A (en) * | 2008-05-28 | 2009-07-29 | 罗德春 | Method for innocent treatment of bottom oil sludge, scruff and active sludge in petro-chemical industry |
| JP2012076047A (en) * | 2010-10-05 | 2012-04-19 | Taiheiyo Cement Corp | Sewage sludge treating method |
| CN111925085A (en) * | 2020-08-25 | 2020-11-13 | 西安德兴环保科技有限公司 | Oil sludge treatment method suitable for heavy bottom oil sludge and tank cleaning oil sludge |
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Denomination of invention: A method for treating high sulfur and high asphalt oil sludge Effective date of registration: 20230718 Granted publication date: 20230321 Pledgee: Xi'an innovation financing Company limited by guarantee Pledgor: Xi'an Dexing Environmental Protection Technology Co.,Ltd. Registration number: Y2023610000590 |
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