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CN114196424A - Recycling treatment method of hazardous waste in pharmaceutical industry - Google Patents

Recycling treatment method of hazardous waste in pharmaceutical industry Download PDF

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Publication number
CN114196424A
CN114196424A CN202111517392.5A CN202111517392A CN114196424A CN 114196424 A CN114196424 A CN 114196424A CN 202111517392 A CN202111517392 A CN 202111517392A CN 114196424 A CN114196424 A CN 114196424A
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China
Prior art keywords
pharmaceutical industry
hazardous waste
recycling
solvent
cracking furnace
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Pending
Application number
CN202111517392.5A
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Chinese (zh)
Inventor
俞孝冬
陈中华
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Zhongye Environmental Protection Technology Chongqing Co ltd
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Zhongye Environmental Protection Technology Chongqing Co ltd
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Priority to CN202111517392.5A priority Critical patent/CN114196424A/en
Publication of CN114196424A publication Critical patent/CN114196424A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D5/00Condensation of vapours; Recovering volatile solvents by condensation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00Other carbonising or coking processes; Features of destructive distillation processes in general
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G7/00Distillation of hydrocarbon oils
    • 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
    • C10G2300/10Feedstock materials
    • C10G2300/1003Waste materials

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a resourceful treatment method of hazardous waste in pharmaceutical industry, which comprises the following steps: (1) conveying the hazardous waste in the pharmaceutical industry into a vacuum drier for drying; (2) condensing the vaporized material by a condenser to obtain a mixed solvent; (3) separating and refining the mixed solvent to obtain a regenerated solvent; (4) crushing the dried residue, mixing the crushed dried residue with a catalyst, and then sending the mixture into a low-temperature cracking furnace for catalytic cracking; (5) condensing the cracked gas by a condenser, and fractionating to obtain fuel oil. The method deeply recovers the residual organic solvent in the hazardous waste of the pharmaceutical industry, further cracks macromolecular organic matters to manufacture fuel oil, recycles the hazardous waste of the pharmaceutical industry, and reduces the discharge of the hazardous waste of the pharmaceutical industry.

Description

Resourceful treatment method for hazardous waste in pharmaceutical industry
Technical Field
The invention belongs to the technical field of hazardous waste treatment, and particularly relates to a resourceful treatment method for hazardous waste in pharmaceutical industry.
Background
China pays great attention to energy conservation and environmental protection, and the treatment requirement on solid wastes, particularly dangerous wastes, is higher and higher. The pharmaceutical industry is an industry that produces a large amount of hazardous waste, and mainly comprises: waste organic solvent, residue of the fine distillation still, centrifugal mother liquor, filtration residue and the like.
The waste organic solvent is easy to be recycled by conventional processes such as distillation, rectification, extraction and the like.
The distillation still residue and the centrifuged mother liquor generally contain macromolecular organic substances (residual drugs, intermediates, reaction by-products, etc.) and impurities such as salts and water, in addition to a part of the organic solvent, because of their complex components. The composition of the organic solvent is also rather complex, with dichloromethane, acetonitrile, methanol, DMF, toluene, THF, ethanol, acetone, etc. being the most commonly used solvents.
At present, the treatment mode of the hazardous waste is mainly incineration. This approach has the following disadvantages:
(1) a large amount of carbon emissions is generated;
(2) dichloromethane and THF are used as precursors for synthesizing dioxin substances, and dioxin can be increased in the process of burning the dangerous wastes;
(3) chlorine-containing organic matters such as dichloromethane and the like generate HCl in the incineration process, generate acid corrosion to equipment, increase the deacidification pressure of tail gas and increase the generation amount of fly ash;
(4) in the incineration process, hazardous wastes containing organic nitrogen, such as acetonitrile, DMF and the like, can generate NOx, so that the pressure of subsequent denitration is increased, and the risk of emission is increased;
(5) the organic solvent is an important chemical raw material, and the direct incineration is also a great waste of resources.
Disclosure of Invention
The invention aims to provide a method for recycling hazardous wastes in the pharmaceutical industry, which is used for deeply recycling residual organic solvents in the hazardous wastes in the pharmaceutical industry, further cracking macromolecular organic matters to manufacture fuel oil, recycling the hazardous wastes in the pharmaceutical industry and reducing the discharge of the hazardous wastes in the pharmaceutical industry.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention discloses a resourceful treatment method of hazardous waste in pharmaceutical industry, which comprises the following steps:
(1) conveying the hazardous waste in the pharmaceutical industry into a vacuum drier for drying;
(2) condensing the vaporized material obtained in the step (1) by a condenser to obtain a mixed solvent;
(3) separating and refining the mixed solvent obtained in the step (2) to obtain a regenerated solvent;
(4) crushing the dried residue obtained in the step (1), mixing the crushed dried residue with a catalyst, and then sending the mixture into a low-temperature cracking furnace for catalytic cracking;
(5) condensing the cracked gas obtained in the step (4) by a condenser, and then fractionating to obtain fuel oil.
As a preferable technical solution, in the step (3), the specific method for separation and purification comprises: the mixed solvent is firstly decanted and layered, and then the liquid phase obtained by layering is classified for solvent refining.
As a preferred technical scheme, the refining comprises one or more of rectification, extraction and membrane separation.
As a preferred technical scheme, if the water content of the liquid phase obtained by layering is more than 95%, the liquid phase is directly treated according to the organic wastewater.
Preferably, in the step (3), the residue generated in the separation and purification process is returned to the vacuum dryer of the step (1) for drying.
Preferably, in the step (4), the catalyst is a mixture of zinc oxide, aluminum hydroxide and graphite.
As a preferable technical scheme, in the step (4), the low-temperature cracking furnace is a vacuum cracking furnace, and the catalytic cracking temperature is as follows: the low temperature region is 200-300 ℃, and the high temperature region is 500-600 ℃.
In the step (5), the residue generated by fractionation is returned to the low-temperature cracking furnace in the step (4) for catalytic cracking.
As a preferred technical scheme, the non-condensable gas generated in the treatment process is collected and then sent back to the low-temperature cracking furnace to be used as fuel.
As a preferred technical scheme, the hazardous waste in the pharmaceutical industry comprises the residue of a fine distillation still or/and a centrifugal mother liquor in the pharmaceutical industry.
The invention has the beneficial effects that:
1. the method adopts vacuum drying to fully and effectively extract the solvent with low boiling point in the hazardous waste in the pharmaceutical industry, and the extracted mixed solvent can be refined to obtain the qualified regenerated solvent; and (4) cracking and fractionating the dried residue at low temperature to obtain qualified fuel oil. The whole process generates a very small amount of secondary hazardous waste, and the resource is very thorough.
2. The invention collects the non-condensable gas generated in the process as the fuel of the low-temperature cracking furnace, so that the VOCs are treated and a large amount of fuel is saved.
3. The invention collects the residues generated in the solvent refining process and then returns the residues to the vacuum drying stage for treatment, thereby really realizing zero emission of hazardous wastes in the recycling process.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The present invention is further described with reference to specific examples to enable those skilled in the art to better understand the present invention and to practice the same, but the examples are not intended to limit the present invention.
As shown in figure 1, the method for recycling hazardous waste in pharmaceutical industry comprises the following steps:
(1) and sampling and detecting the distillation range. The condensing condition of the condenser is determined according to the initial boiling point temperature, the vacuum drying condition (vacuum degree and drying temperature) is determined according to the distillation range, and the low-temperature cracking treatment capacity is determined according to the residue content.
(2) The residue of the fine distillation still and the centrifugal mother liquor in the pharmaceutical industry are sent to a vacuum drier for drying.
(3) Condensing the vaporized material obtained in the step (2) by a condenser to obtain a mixed solvent.
(4) Decanting and layering the mixed solvent obtained in the step (3), classifying the liquid phase obtained by layering (sampling and detecting the type, content and water content of the solvent), and refining the solvent according to the type of the liquid phase, wherein the refining method comprises rectification, extraction, membrane separation and the like to obtain a regenerated solvent; and directly treating the liquid phase with the water content of more than 95% according to the organic wastewater. And (4) returning the residue generated in the separation and purification process to the vacuum drier in the step (1) for drying.
(5) Crushing the dried residue obtained in the step (2), and mixing the crushed dried residue with a catalyst, wherein the catalyst is a mixture consisting of zinc oxide, aluminum hydroxide and graphite; and then sending the mixture into a low-temperature cracking furnace for catalytic cracking, wherein the low-temperature cracking furnace is a vacuum cracking furnace, the catalytic cracking temperature is 200-300 ℃ in a low-temperature region, and the temperature is 500-600 ℃ in a high-temperature region.
(6) Condensing the cracked gas obtained in the step (5) by a condenser, and then fractionating to obtain fuel oil. And (5) returning the residue generated by the fractionation to the low-temperature cracking furnace in the step (5) for catalytic cracking.
(7) And collecting the non-condensable gas generated in the treatment process in the step, and then sending the collected non-condensable gas back to the low-temperature cracking furnace to be used as fuel.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (10)

1.一种制药工业危废的资源化处理方法,其特征在于:包括以下步骤:1. a resource treatment method for hazardous waste in pharmaceutical industry, is characterized in that: comprise the following steps: (1)将制药工业危废送入真空干燥机进行干燥;(1) The hazardous waste of the pharmaceutical industry is sent to a vacuum dryer for drying; (2)将步骤(1)得到的汽化物料经冷凝器冷凝后,得到混合溶剂;(2) after the vaporization material obtained in step (1) is condensed by the condenser, a mixed solvent is obtained; (3)将步骤(2)得到的混合溶剂分离精制,得到再生溶剂;(3) separating and refining the mixed solvent obtained in step (2) to obtain a regenerated solvent; (4)将步骤(1)得到的干燥残渣经过破碎后与催化剂混合,然后送入低温裂解炉进行催化裂解;(4) the dry residue obtained in step (1) is mixed with catalyst after crushing, and then sent to low temperature cracking furnace for catalytic cracking; (5)将步骤(4)得到的裂解气体经冷凝器冷凝后,分馏制得燃油。(5) After the cracked gas obtained in step (4) is condensed by a condenser, fractional distillation is performed to obtain fuel oil. 2.根据权利要求1所述的制药工业危废的资源化处理方法,其特征在于:所述步骤(3)中,分离精制的具体方法为:先将混合溶剂倾析分层,再将分层得到的液相分类进行溶剂精制。2. The method for treating hazardous waste in the pharmaceutical industry according to claim 1, wherein in the step (3), the concrete method for separation and purification is: first the mixed solvent is decanted into layers, and then the The liquid phase obtained by the layer was classified and subjected to solvent purification. 3.根据权利要求2所述的制药工业危废的资源化处理方法,其特征在于:所述精制包括精馏、萃取、膜分离中的一种或几种。3 . The method for recycling hazardous waste in the pharmaceutical industry according to claim 2 , wherein the refining comprises one or more of rectification, extraction and membrane separation. 4 . 4.根据权利要求2所述的制药工业危废的资源化处理方法,其特征在于:分层得到的液相如果含水率大于95%的,直接按有机废水进行处理。4. The method for recycling hazardous wastes in the pharmaceutical industry according to claim 2, characterized in that: if the liquid phase obtained by layering has a water content greater than 95%, it is directly treated as organic waste water. 5.根据权利要求1所述的制药工业危废的资源化处理方法,其特征在于:所述步骤(3)中,分离精制过程产生的残渣重新送回步骤(1)的真空干燥机进行干燥。5. The method for recycling hazardous waste in the pharmaceutical industry according to claim 1, characterized in that: in the step (3), the residue produced in the separation and purification process is sent back to the vacuum dryer of the step (1) for drying. . 6.根据权利要求1所述的制药工业危废的资源化处理方法,其特征在于:所述步骤(4)中,催化剂为氧化锌、氢氧化铝、石墨组成的混合物。6 . The method for treating hazardous waste in the pharmaceutical industry as a resource according to claim 1 , wherein in the step (4), the catalyst is a mixture of zinc oxide, aluminum hydroxide and graphite. 7 . 7.根据权利要求1所述的制药工业危废的资源化处理方法,其特征在于:所述步骤(4)中,低温裂解炉为真空裂解炉,催化裂解温度为:低温区200~300℃,高温区500~600℃。7. The method for treating hazardous waste in the pharmaceutical industry according to claim 1, characterized in that: in the step (4), the low temperature cracking furnace is a vacuum cracking furnace, and the catalytic cracking temperature is: 200~300 ℃ in the low temperature zone , high temperature zone 500 ~ 600 ℃. 8.根据权利要求1所述的制药工业危废的资源化处理方法,其特征在于:所述步骤(5)中,分馏产生的残渣重新送回步骤(4)的低温裂解炉进行催化裂解。8 . The method for recycling hazardous wastes in the pharmaceutical industry according to claim 1 , wherein in the step (5), the residue produced by fractionation is sent back to the low-temperature cracking furnace in the step (4) for catalytic cracking. 9 . 9.根据权利要求1所述的制药工业危废的资源化处理方法,其特征在于:将处理过程中产生的不凝气体收集后送回低温裂解炉用作燃料。9 . The method for recycling hazardous waste in the pharmaceutical industry according to claim 1 , wherein the non-condensable gas generated in the treatment process is collected and returned to the low-temperature cracking furnace to be used as fuel. 10 . 10.根据权利要求1至9任意一项所述的制药工业危废的资源化处理方法,其特征在于:所述制药工业危废包括制药工业的精蒸馏釜残或/和离心母液。10 . The method for recycling hazardous waste in the pharmaceutical industry according to any one of claims 1 to 9 , wherein the hazardous waste in the pharmaceutical industry comprises fine distillation still residues or/and centrifugal mother liquor in the pharmaceutical industry. 11 .
CN202111517392.5A 2021-12-13 2021-12-13 Recycling treatment method of hazardous waste in pharmaceutical industry Pending CN114196424A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101767920A (en) * 2008-12-30 2010-07-07 新疆华易石油工程技术有限公司 Oil field oil sludge treatment method
CN102335668A (en) * 2010-07-19 2012-02-01 车磊 Method for treating industrial hazardous wastes containing organic solvent
CN102604662A (en) * 2012-03-21 2012-07-25 河北工业大学 Process for finely recovering and recycling oil products from pyrolysis gas in process of converting waste plastic into oil
CN103980921A (en) * 2014-05-29 2014-08-13 曹文祥 Process for producing fuel oil by thermal cracking of biomass
CN206019277U (en) * 2016-08-30 2017-03-15 江苏先锋干燥工程有限公司 Vacuum belt drier solvent recovering system
CN107312568A (en) * 2017-06-27 2017-11-03 爱润森德(天津)能源科技有限公司 A kind of waste mineral oil catalytic pyrolysis utilization system and its processing technology
CN107400530A (en) * 2017-06-30 2017-11-28 河南地之绿环保科技有限公司 A kind of process of waste old fuel oil
CN112316468A (en) * 2020-11-04 2021-02-05 杭州索孚化工工程技术有限公司 Method for treating still residue and waste salt
CN113546946A (en) * 2021-07-23 2021-10-26 浙江中蓝环境科技有限公司 Anaerobic dry distillation treatment method for medical waste

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101767920A (en) * 2008-12-30 2010-07-07 新疆华易石油工程技术有限公司 Oil field oil sludge treatment method
CN102335668A (en) * 2010-07-19 2012-02-01 车磊 Method for treating industrial hazardous wastes containing organic solvent
CN102604662A (en) * 2012-03-21 2012-07-25 河北工业大学 Process for finely recovering and recycling oil products from pyrolysis gas in process of converting waste plastic into oil
CN103980921A (en) * 2014-05-29 2014-08-13 曹文祥 Process for producing fuel oil by thermal cracking of biomass
CN206019277U (en) * 2016-08-30 2017-03-15 江苏先锋干燥工程有限公司 Vacuum belt drier solvent recovering system
CN107312568A (en) * 2017-06-27 2017-11-03 爱润森德(天津)能源科技有限公司 A kind of waste mineral oil catalytic pyrolysis utilization system and its processing technology
CN107400530A (en) * 2017-06-30 2017-11-28 河南地之绿环保科技有限公司 A kind of process of waste old fuel oil
CN112316468A (en) * 2020-11-04 2021-02-05 杭州索孚化工工程技术有限公司 Method for treating still residue and waste salt
CN113546946A (en) * 2021-07-23 2021-10-26 浙江中蓝环境科技有限公司 Anaerobic dry distillation treatment method for medical waste

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