CN107456775A

CN107456775A - For reclaiming the method and system of VOC

Info

Publication number: CN107456775A
Application number: CN201610389920.6A
Authority: CN
Inventors: 修国华
Original assignee: Shanghai Whale Technology Development Co Ltd
Priority date: 2016-06-03
Filing date: 2016-06-03
Publication date: 2017-12-12

Abstract

The application is related to for reclaiming VOC（VOCs）Method and system.It effectively reclaims VOCs by adsorption treatment and condensation process, so as to reduce VOCs discharge, on the basis of reducing environmental pollution, also further to utilize VOCs.

Description

For reclaiming the method and system of VOC

Technical field

The application is related to the recycling of organic compound, more particularly to the side for reclaiming VOC Method and system.

Background technology

VOC (volatile organic compounds, VOCs) is the row such as oil, pharmacy, printing The common contaminant of industry discharge.VOCs materials human health multipair greatly has negative effect, but these materials are again more after recovery Number has economic value, does not only have considerable economic benefit so reclaimed and be used to it, to the meaning of environmental protection Justice is also very great.

In China, with the rapid development of economy, just becoming increasingly stronger for the demand of environmental protection, and for The administering method of VOCs pollutions also has become a study hotspot.But because VOCs generally existings composition composition complexity etc. is asked Topic, so further lifting VOCs organic efficiency for the new devices, systems, and methods of continual exploitation and reducing cost Still there is active demand.

The content of the invention

This application provides the method and system for reclaiming VOC (VOCs), described method and system VOCs can be effectively reclaimed, so as to reduce VOCs discharge, on the basis of reducing environmental pollution, also further to utilize VOCs is possibly realized.

On the one hand, this application provides a kind of method for being used to reclaim VOC (VOCs).This method can With including：The pending fluid comprising VOCs is set to obtain VOCs condensate liquids through adsorption treatment and condensation process.The condensation Liquid low temperature cooling medium, the volatilizable generation inert gas of liquid low temperature cooling medium, and the inert gas can be used At least a portion can be used for regeneration and/or the regulation pending stream for including VOCs of sorbing material in the absorption Oxygen content in body.The liquid low temperature cooling medium can be liquid nitrogen.The inert gas can be nitrogen.

In some embodiments of this method, before the condensation process, it can make described pending to include VOCs Fluid be subjected to the adsorption treatment.In some embodiments of this method, after the condensation process, it may be such that Not solidifying fluid through the adsorption treatment.

In some embodiments of this method, make the pending fluid comprising VOCs through adsorption treatment and cold Before solidifying processing, the oxygen content in the pending fluid comprising VOCs can detect.After the oxygen content is detected and , can be to the pending bag before the pending fluid comprising VOCs is made through the adsorption treatment and condensation process Fluid containing VOCs is compressed.

In some embodiments, make the pending fluid comprising VOCs through the adsorption treatment and condensation at Before reason, the pending fluid comprising VOCs is compressed.

In the present processes, the adsorption treatment may include to use pressure-variable adsorption, temp.-changing adsorption and/or pressure and temperature varying Absorption.

In the present processes, the adsorption treatment can produce unadsorbed fluid (absorption tail gas), and described unadsorbed At least a portion of fluid (absorption tail gas) can be used for the regeneration of sorbing material in the absorption and/or adjust described pending The fluid comprising VOCs in oxygen content.

In certain embodiments, the present processes are used for petroleum vapor recovery.

In another aspect, the application is related to a kind of system for being used to reclaim VOC (VOCs).It is described System may include condensing unit and absorbing unit to handle the fluid for including VOCs.The condensing unit can be with the absorbing unit It is in fluid communication.The condensing unit can include to be situated between using the condensing unit of liquid low temperature cooling medium and liquid low temperature condensation Matter volatilization produces inert gas.The inert gas can with the absorbing unit be in fluid communication and the inert gas at least one Part can be used for the regeneration of sorbing material in the absorbing unit, and/or the inert gas can be with the pending bag Be in fluid communication between fluid containing VOCs and at least a portion of the inert gas can with it is pending described in include VOCs stream Body is mixed to adjust oxygen content therein.

In the system of the application, the liquid low temperature cooling medium can be liquid nitrogen.The inert gas can be nitrogen.

In the system of the application, the condensing unit and the absorbing unit may be set so that pending described Fluid comprising VOCs is subjected to the absorbing unit before being handled through the condensing unit and handled.

In the system of the application, the condensing unit may be set so that through the condensation with the absorbing unit After cell processing, obtained not solidifying fluid is handled through the absorbing unit.

The system of the application may include oxygen probe, the oxygen probe can be used for make it is pending described in comprising VOCs Fluid is handled with before condensing unit processing through the absorbing unit, detects the oxygen in the pending fluid comprising VOCs Content.

May include compression unit in the system of the application, the compression unit can be arranged to detect the oxygen content it Afterwards, and make it is pending described in before the fluid comprising VOCs enters the absorbing unit and condensing unit, to pending The fluid comprising VOCs is compressed.

In some embodiments, the system of the application also includes compression unit, and the compression unit is arranged to make The pending fluid comprising VOCs enters before the absorbing unit and condensing unit, to including described in pending VOCs fluid is compressed.

In the system of the application, the absorbing unit may include psa unit, temperature swing adsorption unit, and/or become Press temperature swing adsorption unit.The absorbing unit can produce unadsorbed fluid (absorption tail gas), unadsorbed fluid (the absorption tail Gas) can with it is pending described in comprising VOCs fluid between be in fluid communication and the unadsorbed fluid (absorption tail gas) at least one Part can with it is pending described in mix to adjust oxygen content therein, and/or the unadsorbed fluid comprising VOCs fluid (absorption tail gas) can be in fluid communication with the absorbing unit and at least a portion of the unadsorbed fluid is used for the absorption The regeneration of sorbing material in unit.

In the system of the application, the condensing unit may include following one or more assemblies：It is one or more cold Condenser (for example, precondenser, first-stage condenser, secondary condenser etc.), storage tank, oil water separator, layering groove, vavuum pump, wind Machine and compressor.

The system of the application can be used for petroleum vapor recovery or can be the part of gas recovery system for oil.

Those skilled in the art can from detailed description below in easily have insight into the other side of the disclosure and excellent Gesture.The illustrative embodiments of the disclosure only have been shown and described in detailed description below.As those skilled in the art will recognize Know, content of this disclosure enables those skilled in the art to be modified to disclosed embodiment without de- From the spirit and scope invented involved by the application.Correspondingly, the description in the drawing and description of the application is only example Property, rather than be restricted.

Brief description of the drawings

The specific features of invention involved by the application are as shown in appended claims.By reference in more detail below The illustrative embodiments and accompanying drawing of description better understood when the application involved the characteristics of inventing and advantage.To accompanying drawing letter Want specification as follows：

Fig. 1 shows the schematic diagram of an example of system provided herein.

Fig. 2 shows the schematic diagram of an example of system provided herein.

Embodiment

Illustrate the embodiment of the present application by particular specific embodiment below, those skilled in the art can be by this Specification disclosure of that is easily realized by other advantages and effect of the present application.

In this application, " VOC (VOCs, volatile organic compounds) " is often referred to (101.3kPa) initial boiling point (initial boiling point) is not higher than the change of 250 DEG C (482 ℉) at normal atmospheric pressure Compound.For example, meet various alkanes of above-mentioned standard, various aromatic hydrocarbons, various halohydrocarbons, various esters, various aldehydes, various Ketone, various alcohols, various ethers, various phenols, various epoxies, various esters, various acids, various amines, various nitriles Class compound etc..For example, the one or more in following material can be included in the VOCs：Cyclohexanone, isophorone, methanol, Ethanol, phenol, acetone, ethyl acetate, benzene, n-butanol, methyl iso-butyl ketone (MIBK), n-butyl acetate, ortho-xylene, meta-xylene, Paraxylene, toluene, styrene, 1,2- dichloro-benzenes, acetophenone, MEK, isopropanol, dichloromethane, trichloro ethylene, ethylbenzene, Ethane, butane, propane, pentane, n-hexane, 2- ethyl methoxyacetates, nitrobenzene, double (2- methoxy ethyls) ethers and 1,3,5- Trimethylbenzene etc..

In this application, " initial boiling point " is often referred to a kind of steam pressure of liquid and is equal to standard atmospheric pressure (101.3kPa) When, temperature when first bubble occurs.

In this application, " fluid " be often referred to fixed mass and the object without solid shape, such as liquids and gases.

In this application, " cryogenic condensation medium " is often referred to meet by heat exchange pending gas and/or liquid Cold and condensation material.For example, the cryogenic condensation medium in the application can be liquid nitrogen, liquid argon, liquid CO 2 etc..

In this application, " inert gas " be often referred to be not easy with the pending fluid and/or air comprising VOCs The gaseous material that main component (such as oxygen, VOCs etc.) chemically reacts.For example, the inert gas may include but unlimited In：Nitrogen, CO₂Or argon gas etc., or their any combination.

In this application, " adsorption treatment " is often referred to the physical absorption using adsorbent and/or chemisorbed performance, passes through The method that adsorbent realizes separation for the difference of the adsorption capacity of different component in mixture.It is not intended to be bound by theory, During the adsorption treatment, (such as pressed to realize that circulate operation can be regenerated to used adsorbent by adjusting Power and/or temperature).For example, the adsorption treatment may include pressure-variable adsorption, temp.-changing adsorption and/or alternating temperature pressure-variable adsorption etc..

In this application, " condensation process " be often referred to by cryogenic condensation medium and pending gas and/or liquid it Between heat exchange, the process for making part or all of component in pending gas and/or liquid to the cold and condensing.

In this application, " liquid nitrogen " is often referred to the liquid form of nitrogen, and " liquid argon " is often referred to the liquid form of argon gas, " liquid Body carbon dioxide " is often referred to the liquid form of carbon dioxide.

In this application, " pressure-variable adsorption " is typically for different in mixture (such as admixture of gas) using adsorbent Characteristic that the difference of the adsorption capacity of component changes in pressure change and the method for realizing separation.For example, pressure-variable adsorption The pressure-variable adsorption based on balancing effect, the pressure-variable adsorption based on kinetic effect and the transformation based on steric effect can be included Absorption etc..Pressure-variable adsorption based on balancing effect is typically the difference using different component molecule equilibrium adsorption capacity on the sorbent Separated.It is to be diffused into according to different component molecule in adsorbent pores that pressure-variable adsorption based on kinetic effect, which is typically, Speed is different, appropriate to select the adsorbance of adsorption time control targe component and non-target components to realize separation.Based on steric hindrance The pressure-variable adsorption of effect is typically that the difference of the steric effect of each group fractionated molecule is realized and divided using micropore in absorbent particles From.

In this application, " temp.-changing adsorption " is typically for different in mixture (such as admixture of gas) using adsorbent Characteristic that the difference of the adsorption capacity of component changes in temperature change and the method for realizing separation.

In this application, " pressure and temperature varying absorption " is typically in mixture (such as admixture of gas) using adsorbent Characteristic that the difference of the adsorption capacity of different component changes in pressure and temperature change and the method for realizing separation.

In this application, term " about " typically refers to specifying numerical value above and below 0.5%-1.5% excursion It is interior.

In this application, " fluid communication " is often referred to that between two or more devices the fluid in a device can be introduced In another device.

In this application, " compression " typically refers to make the reduction of the volume of fluid and/or pressure increase by applying pressure Process.In this application, compression ratio can be caused by the compression, for example, no more than 3, no more than 2.5, no more than 2 or No more than 1.5.Compression can be realized by various appropriate means, for example, air blower, air exhauster and/or compression can be passed through Machine realizes compression.

Method for reclaiming VOC

On the one hand, the application provides a kind of method for being used to reclaim VOC (VOCs).

Methods described can include making the pending fluid comprising VOCs obtain through adsorption treatment and condensation process VOCs condensate liquids.Liquid low temperature cooling medium, the volatilizable generation inertia of liquid low temperature cooling medium can be used in the condensation Gas.At least a portion of the inert gas can be used for treating described in the regeneration and/or regulation of sorbing material in the absorption Oxygen content in the fluid comprising VOCs of processing.In some embodiments, in the pending fluid comprising VOCs Oxygen content be adjusted to safety limit less than oxygen.In this application, " safety limit of oxygen " is often referred to containing fuel gas The content of oxygen, which is not higher than, in mixed gas causes burning and/or the limit value to explode or outside the explosion limit of oxygen.For example, In the mixed gas comprising methane, the safety limit of oxygen can be no more than about 15%, no more than about 14%, no more than about 13%, no more than about 12%, no more than about 11.5%, no more than about 11%, no more than about 10.5%, no more than about 10%, no Greater than about 9.5%, no more than about 9%, no more than about 8%, no more than about 7%, no more than about 6%, no more than about 5% is not high In about 4%, no more than about 3%, no more than about 2%, no more than about 1%, no more than about 0.5% or lower.For example, it can pass through Adjust the content of inert gas in the mixed gas and the oxygen content in the pending fluid comprising VOCs is existed The safety limit scope of the oxygen or outside the explosion limit of oxygen.

In some embodiments, before the condensation process, the pending fluid comprising VOCs is made to be subjected to institute State adsorption treatment.The pending fluid comprising VOCs can be initially subjected to adsorption treatment, and the adsorption treatment, which produces, does not inhale Attached fluid, unadsorbed fluid can be used as absorption tail gas (for example, tail gas up to standard), and adsorbed part can be desorbed to obtain The fluid for including VOCs after adsorption treatment, the fluid comprising VOCs after adsorption treatment can be further subjected to cold Solidifying processing, and VOCs condensate liquids can be obtained by condensation process.In some embodiments, can be obtained not after condensed processing Solidifying fluid, the not solidifying fluid can be made to be subjected to adsorption treatment again, and unadsorbed fluid can be used as tail gas up to standard.

In some embodiments, after the condensation process, so as to get not solidifying fluid through the absorbing unit Processing.The pending fluid comprising VOCs can be initially subjected to condensation process, and can obtain VOCs condensate liquids and/or not Solidifying fluid, the not solidifying fluid can be subjected to adsorption treatment again, and unadsorbed fluid can be used as tail gas up to standard.

In some embodiments, make the pending fluid comprising VOCs through adsorption treatment and condensation process it Before, detect the oxygen content in the pending fluid comprising VOCs.In the pending fluid comprising VOCs is obtained Oxygen content after, can be adjusted by least a portion of the inert gas in the pending fluid comprising VOCs Oxygen content.

In some embodiments, after the oxygen content is detected, and the pending stream for including VOCs is made Before body is through the adsorption treatment and condensation process, the pending fluid comprising VOCs is compressed.In some realities Apply in mode, the pending fluid comprising VOCs can be made to be initially subjected to condensation process.Before the condensation process, and It has detected and (adjusted by using for example described inert gas after the oxygen content in the pending fluid comprising VOCs Section, the oxygen content is set to be adjusted to the safety limit less than oxygen), can be by the pending fluid compression comprising VOCs extremely Its pressure is not less than about 0.01MPa, not less than about 0.05MPa, not less than about 0.1MPa, not less than about 0.15MPa, is not less than About 0.2MPa, not less than about 0.25MPa, not less than about 0.3MPa, not less than about 0.4MPa, not less than about 0.5MPa, are not less than About 0.6MPa, not less than about 0.8MPa, or not less than about 1.0MPa.For example, in some embodiments, the boil down to one-level Compression or two stages of compression.In some embodiments, the compression ratio of the compression is for example, no more than 3, no more than 2.5, less In 2, or no more than 1.5.

In some embodiments, the unadsorbed fluid of the adsorption treatment generation, at least one of the unadsorbed fluid The oxygen content divided in the regeneration for being used for sorbing material in the absorption or the regulation pending fluid comprising VOCs.

In the present processes, in the pending fluid comprising VOCs, VOCs can include but is not limited to：Alkane Class, aromatic hydrocarbons, halohydrocarbon, esters, aldehydes, ketone, alcohols, ethers, phenols, epoxies, esters, acids, amine, nitrile etc., Or their any combination.The alkanes can include but is not limited to：Butane, n-hexane etc., or their any combination； The aromatic hydrocarbons can include but is not limited to：Benzene,toluene,xylene, styrene etc., or their any combination；The halogen Hydro carbons can include but is not limited to：Dichloromethane, chloroform, trichloroethanes, dichloroethylene, trichloro ethylene, tetrachloro-ethylene, four Chlorination carbon, methyl bromide, CFC, hydrochlorofluorocarsolvent etc., or their any combination；The aldehydes can include but unlimited In：Formaldehyde, acetaldehyde etc., or their any combination；The ketone can include but is not limited to：Acetone, butanone, cyclohexanone, Methyl iso-butyl ketone (MIBK) etc., or their any combination；The alcohols can include but is not limited to：Methanol, isopropanol, isobutanol Deng, or their any combination；Ethers can include but is not limited to：Ether etc.；Phenols can include but is not limited to：Cresols, Phenol etc., or their any combination；Epoxies can include but is not limited to：Oxirane, expoxy propane etc., or they Any combination；Esters can include but is not limited to：Ethyl acetate, butyl acetate etc., or their any combination；Acids can To include but is not limited to：Acetic acid etc.；Amine can include but is not limited to：Dimethylformamide etc.；Nitrile can include but unlimited In：Acrylonitrile etc..In the pending fluid comprising VOCs, VOCs concentration can be 700g/m³More than, 600g/m³With On, 500g/m³More than, 400g/m³More than, 300g/m³More than, 200g/m³More than, 150g/m³More than, 100g/m³More than, 70g/ m³More than, 50g/m³More than, 40g/m³More than, 30g/m³More than, 20g/m³More than, 10g/m³More than, 7g/m³, 5g/m³More than, 4g/m³More than, 3g/m³More than, 2g/m³More than, 1g/m³More than, 800mg/m³More than, 600mg/m³More than, 400mg/m³More than, 200mg/m³More than, 100mg/m³More than, 80mg/m³More than, 60mg/m³More than, 40mg/m³More than, 20mg/m³More than, 10mg/ m³More than, 8mg/m³More than, 6mg/m³More than, 5mg/m³More than, 4mg/m³More than, 3mg/m³More than, 2mg/m³More than, 1mg/m³ More than, or 0.5mg/m³More than；VOCs flow can be 600000m³/ more than h, 500000m³/ more than h, 400000m³/ h with On, 300000m³/ more than h, 200000m³/ more than h, 100000m³/ more than h, 70000m³/ more than h, 50000m³/ more than h, 30000m³/ more than h, 20000m³/ more than h, 10000m³/ more than h, 7000m³/ more than h, 5000m³/ more than h, 4000m³/ h with On, 3000m³/ more than h, 2000m³/ more than h, 1000m³/ more than h, 900m³/ more than h, 800m³/ more than h, 700m³/ more than h, 600m³/ more than h, or 500m³/ more than h, 400m³/ more than h, 300m³/ more than h, 200m³/ more than h, 100m³/ more than h, 50m³/ More than h, 30m³/ more than h, 20m³/ more than h, 10m³/ more than h, or 5m³/ more than h.Those skilled in the art can be according to VOCs Flow and/or concentration determine first to be condensed and adsorbed again, still first adsorbed and condensed again.For example, work as VOCs Concentration is not more than 5000mg/m³, no more than 4000mg/m³, no more than 3000mg/m³, no more than 2000mg/m³, it is not more than 1000mg/m³, no more than 500mg/m³, no more than 400mg/m³, no more than 100mg/m³, no more than 50mg/m³, it is not more than 20mg/m³, no more than 10mg/m³, no more than 5.0mg/m³, no more than 1.0mg/m³, no more than 0.5mg/m³, no more than 0.2mg/ m³, no more than 0.1mg/m³, no more than 0.05mg/m³, no more than 0.01mg/m³, or no more than 0.3mg/m³When, can first it carry out Absorption is condensed again；For another example when VOCs concentration is not less than 1000g/m³, not less than 800g/m³, not less than 500g/m³, no Less than 300g/m³, not less than 200g/m³, not less than 100g/m³, not less than 50g/m³, or not less than 10g/m³When, can be with advanced Row condensation is adsorbed again；For another example when VOCs flow is not more than 300000m³During/h, no more than 200000m³During/h, less In 100000m³During/h, no more than 80000m³During/h, no more than 60000m³During/h, no more than 40000m³During/h, it is not more than 20000m³During/h, no more than 10000m³During/h, no more than 8000m³During/h, no more than 6000m³During/h, no more than 4000m³/h When, no more than 2000m³During/h, no more than 1000m³During/h, no more than 900m³During/h, no more than 800m³During/h, it is not more than 700m³During/h, no more than 600m³During/h, no more than 500m³During/h, no more than 400m³During/h, no more than 300m³During/h, less In 200m³During/h, no more than 100m³During/h, no more than 90m³During/h, no more than 80m³During/h, no more than 70m³During/h, it is not more than 60m³During/h, or no more than 50m³During/h, it can first be condensed and be adsorbed again；For another example when VOCs flow is not less than 100m³During/h, not less than 200m³During/h, not less than 300m³During/h, not less than 400m³During/h, not less than 500m³It is not small during/h In 600m³During/h, not less than 700m³During/h, not less than 800m³During/h, not less than 900m³During/h, not less than 10000m³During/h, Not less than 12000m³During/h, not less than 14000m³During/h, not less than 18000m³/ h, not less than 20000m³During/h, or it is not less than 30000m³During/h, it can first be adsorbed and be condensed again.

In the present processes, the condensation process can use such as wall-type heat exchange method, fluidly connect indirect type Heat exchange method etc.." the wall-type heat exchange method " is often referred to two kinds of different fluids of temperature and flowed in the space separated by wall, Exchanged heat by the heat conduction and fluid of wall between wall surface convection current, two kinds of fluids.For example, make cooling medium and pending The fluid comprising VOCs flowed in the space separated by wall, can be by the heat conduction and fluid of wall in wall surface Convection current, cooling medium can partly or entirely be gasified after absorbing heat, the pending fluid heat quilt comprising VOCs Temperature reduces after absorption." the fluidly connecting indirect type heat exchange method " is often referred to two surface-type heat exchangers by circulating wherein The method that connects of heat carrier (for example, refrigerant), heat carrier circulates between high temperature fluid heat exchanger and cryogen, Receive heat from high temperature fluid, heat is released to cryogen at cryogen heat exchanger.The heat exchanger can be example Such as coil exchanger, tubular heat exchanger (such as Dual-tube heat exchanger), plate-fin heat exchanger, accumulation of heat material filling type heat exchanger are filled out Expect (column plate) formula heat exchanger.For example, low temperature using cooling medium partly or entirely gasify when absorption refrigeration agent heat, be condensed Refrigerant after Absorption of Medium heat be further used for absorb comprising VOCs fluid heat, so as to realize cooling medium with The method of heat exchange between fluid comprising VOCs.

During the condensation process, the cryogenic condensation medium, which can produce, can make the liquefied low temperature of VOCs, pass through Heat exchange between fluid comprising VOCs and cryogenic condensation medium so that the VOCs component liquefactions in the fluid comprising VOCs, So as to obtain VOCs condensate liquids, and cryogenic condensation medium can volatilize and produce inert gas.In the condensation process, it can produce Raw not coagulate fluid, the not solidifying fluid can be further subjected to adsorption treatment.Those skilled in the art can according to VOCs species, It is determined to make the liquefied low temperature of VOCs.It is not intended to be bound by theory, however, for same VOC components, with partial pressure Reduce, its condensing temperature can be reduced correspondingly.For example, at normal atmospheric pressure, the low temperature that dichloromethane liquefies can be made for not Temperature higher than 39.8 DEG C；At normal atmospheric pressure, the liquefied low temperature of toluene can be made for the temperature not higher than 110.6 DEG C. The cryogenic condensation medium that can be used in condensation process includes but is not limited to, for example, liquid nitrogen, liquid argon and liquid CO 2 etc. with And their mixture.The inert gas that can be obtained in condensation process includes but is not limited to, such as nitrogen, argon gas, dioxy Change carbon etc. and their mixture.The inert gas is generally the corresponding gas form of cryogenic condensation medium, for example, when low When warm cooling medium can be liquid nitrogen, inert gas caused by its volatilization can be nitrogen.

In the present processes, the cryogenic temperature of the cryogenic condensation medium can be, such as -70 DEG C to -160 DEG C, Such as less than -70 DEG C, less than -80 DEG C, less than -90 DEG C, less than -100 DEG C, less than -110 DEG C, less than -120 DEG C, -130 DEG C with Under, less than -140 DEG C, less than -150 DEG C, or -160 DEG C such as the following.In a particular embodiment, the cryogenic condensation medium Cryogenic temperature can be, such as -90 DEG C to -160 DEG C, -95 DEG C to -160 DEG C, -100 DEG C to -160 DEG C, -105 DEG C to -160 DEG C, -110 DEG C to -160 DEG C, -120 DEG C to -160 DEG C, -130 DEG C to -160 DEG C, -140 DEG C to -160 DEG C, -150 DEG C to -160 DEG C Deng.

During the condensation process, can make the fluid containing VOCs sequentially pre-cooled condenser, first-stage condenser and/ Or secondary condenser processing, and obtain VOCs condensate liquids.For example, in some embodiments of the application, it is described containing VOCs's Fluid sequentially after pre-cooled condenser, first-stage condenser, and/or secondary condenser processing, respectively obtains VOCs condensate liquids successively.

In this application, described " adsorption treatment " can include, such as pressure-variable adsorption, temp.-changing adsorption and/or alternating temperature transformation Absorption etc., as other parts are described in detail in the application.In some embodiments of the application, the adsorption treatment does not include Electrolysis is inhaled.In some embodiments of the application, the adsorption treatment is not including the use of NACF as absorption material Electrolysis inhale.In adsorption treatment, the adsorbent that can be used includes but is not limited to, such as activated carbon, carbon molecular sieve, natural boiling Stone, modified zeolite (such as sial based molecular sieve), silica gel, modified silica-gel, mesopore molecular sieve, titanium-based molecular sieve, metal have machine frame Frame material and their mixture.In some embodiments, the adsorbent does not include NACF.In some realities Apply in mode, the adsorbent includes activated carbon granule.In some embodiments, the adsorbent includes molecular sieve.It is described In adsorption treatment, for example, VOCs components in the fluid comprising VOCs can be adsorbed using adsorbent under conditions of low temperature, high pressure, Unadsorbed part can be unadsorbed fluid, and can be desorbed in the case of high temperature and/or low pressure to realize sorbing material Regeneration.At least a portion of the stripping gas obtained in the application some embodiments, during regneration of adsorbent material can enter one Step is subjected to condensation process, to obtain VOCs condensate liquids.

In this application, the renovation process of sorbing material can be the method for separating adsorbed material and adsorbent, For example, the methods of heating, being depressured, purged using gas.In the application some embodiments, renovation process can be using again The adsorbent of angry body purging absorption on the adsorbent material, the regeneration gas can include liquid low temperature cooling medium and volatilize At least a portion of caused inert gas, the inert gas of external source can also be included, such as may include but be not limited to：Nitrogen, Carbon dioxide, argon gas, and/or air etc., or their any combination.In some embodiments of the application, it is described again Angry body can include at least a portion of the unadsorbed fluid (for example, absorption tail gas).

In some embodiments, the adsorption treatment includes adsorption process and desorption process.The desorption process can wrap Include and desorbed using Vacuum solutions sucking pump and purged using regeneration gas.For example, the desorption process may include：First pass through true Sky desorption pumping vacuum is for a period of time (for example, more than 0.1 minute, more than 1 minute, more than 5 minutes, more than 10 minutes, 15 minutes More than, more than 20 minutes, more than 25 minutes, more than 30 minutes, more than 35 minutes, more than 40 minutes, more than 45 minutes, 50 minutes More than, such as 5-50 minutes, 10-40 minutes, 15-30 minutes etc.), subsequently or simultaneously using regeneration gas (for example, the institute through volatilization State inert gas, such as nitrogen) purged；Then with the regeneration gas of heating (for example, the indifferent gas through volatilization Body, such as nitrogen) purged (for example, pulsed purging)；Afterwards with the regeneration gas (for example, described lazy through volatilization Property gas, such as nitrogen) the cooling absorbing unit (for example, adsorption bed).(example is being purged with the regeneration gas of heating Such as, impulse blowing) when, the inlet temperature of the regeneration gas of the heating can be not less than about 90 degrees Celsius, not less than about 95 Degree Celsius, it is Celsius not less than about 115 not less than about 110 degrees Celsius not less than about 105 degrees Celsius not less than about 100 degrees Celsius Degree, not less than about 120 degrees Celsius, not less than about 125 degrees Celsius, not less than about 130 degrees Celsius, not less than about 135 degrees Celsius, no Below about 140 degrees Celsius, not less than about 150 degrees Celsius, not less than about 160 degrees Celsius, not less than about 170 degrees Celsius, it is not less than About 180 degrees Celsius, not less than about 190 degrees Celsius, not less than 200 degrees Celsius, not less than about 210 degrees Celsius, or not less than about 220 Degree Celsius.For example, the inlet temperature of the regeneration gas of the heating can be about about 145 degrees Celsius of 95- or about 100- about 140 takes the photograph Family name's degree.For example (for example, not higher than 55 degrees Celsius, taken the photograph when the gas temperature in exit reaches not higher than 60 degrees Celsius not higher than 50 Family name's degree, not higher than 45 degrees Celsius, not higher than 40 degrees Celsius, or not higher than 35 degrees Celsius) when stop entrance described in heat again The entrance of angry body, and start to cool down the adsorption system.In some embodiments, in the desorption process, Before by vacuum desorption pumping vacuum, can first with the regeneration gas (for example, the inert gas through volatilization, such as Nitrogen) purging a period of time (for example, more than 2 minutes, more than 5 minutes, more than 10 minutes, more than 15 minutes, more than 20 minutes, More than 25 minutes, more than 30 minutes, such as 2-30 minutes, 5-30 minutes, 5-20 minutes, 10-20 minutes etc.).The application's is described Adsorption treatment process greatly reduces energy consumption and improves the operating efficiency of system.

In this application, the unadsorbed fluid can be used as absorption tail gas (for example, tail gas up to standard), the tail gas up to standard The content for referring generally to its VOCs meets for example, domestic GB 21902-2008, DB11/139-2015, DB11/447-2015, DB11/1201-2015, DB11/1202-2015, DB11/1203-2015, DB 31/374-2006 and/or European Union 1996/61/ The standards such as EC, 1999/13/EC, 2004/42/EC.For example, the content of NMHC is not higher than in the tail gas up to standard 600mg/m³, not higher than 500mg/m³, not higher than 400mg/m³, not higher than 300mg/m³, not higher than 200mg/m³, or be not higher than 100mg/m³, not higher than 80mg/m³, not higher than 60mg/m³, not higher than 50mg/m³, not higher than 20mg/m³, or not higher than 10mg/ m³；It can also be for example, toluene level is not higher than 100mg/m³, not higher than 80mg/m³, not higher than 70mg/m³, not higher than 60mg/ m³, not higher than 50mg/m³, not higher than 40mg/m³, or not higher than 30mg/m³；It can also be for example, xylene content is not higher than 200mg/m³, not higher than 160mg/m³, not higher than 120mg/m³, not higher than 100mg/m³, not higher than 80mg/m³, not higher than 60mg/ m³, not higher than 40mg/m³, or not higher than 20mg/m³；It can also be for example, benzene content is not higher than 20mg/m³, not higher than 15mg/ m³, not higher than 10mg/m³, not higher than 8mg/m³, not higher than 6mg/m³, not higher than 4mg/m³, or not higher than 2mg/m³。

In this application, normally, in VOCs content and/or concentration, mass unit (for example, g, mg etc.) shows to wrap NMHC is (for example, eliminate methane, water, N in fluid containing VOCs₂、O₂、CO₂Total hydrocarbon) quality, and m³It is to include The volume of the fluid comprising VOCs of all components.

In some embodiments, at least a portion of the unadsorbed fluid (for example, absorption tail gas) can be used for The pending fluid comprising VOCs is mixed to adjust oxygen content therein.For example, the oxygen content can be adjusted to that it is low In the safety limit of oxygen.For example, cause the content of oxygen in the pending fluid comprising VOCs is not higher than to draw after mixing Combust and/or the limit value of blast.For example, wherein the content of oxygen can be no more than about 15%, no more than about 14%, it is not high In about 13%, no more than about 12%, no more than about 11.5%, no more than about 11%, no more than about 10.5%, no more than about 10%, no more than about 9.5%, no more than about 9%, no more than about 8%, no more than about 7%, no more than about 6%, no more than about 5%, no more than about 4%, no more than about 3%, no more than about 2%, no more than about 1%, no more than about 0.5% or lower.

In this application, inert gas caused by the liquid low temperature cooling medium volatilization is used directly for subsequently walking Suddenly, it can also be stored in inert gas storage unit and use when needed.The inert gas storage unit includes inertia Gas storage device, the inert gas storage device can be that the gas for storing and/or receiving suitable for inert gas stores Device, it may include such as metal tank, nonmetallic storage tank and metal and nonmetal composite storage tank.For example, the metal tank can Including carbon steel storage tank, stainless steel storage tank and aluminium storage tank etc., the nonmetallic storage tank may include plastic storage tank, ceramic storage tank and glass Steel tank etc., the metal and nonmetal composite storage tank may include steel lining tetrafluoro storage tank, steel lining polyethylene storage tank, the storage of steel lining polyolefin Tank, steel lining glue storage tank etc..Can also it is determined that the parameter such as pressure store, storage time, storage volumes needed for storage device with The design parameter of storage device is determined afterwards, and the design parameter of GB150-1998 is such as determined according to GB150-2011.

The methods described of the application can be used for such as petroleum vapor recovery.The present processes can be additionally used in following one or more During VOCs recovery：Oil refining production, petrochemicals production, organic chemistry raw material production (such as solvent production), change Learn production of raw medicine, oil depot accumulating, oil tank accumulating, chemicals storage, chemicals transhipment, chemicals dispatching, paint production and make Produce and make with the production of, building coating and using, Printing ink producing and using, Polymer Synthesizing, food production and using, commodity With, pesticide producing and use, Feed Manufacturing and use, Tire production, fuel combustion, smelting iron and steel, textile printing and dyeing, papermaking, vapour Car manufacture, shipbuilding, aircraft manufacturing, household electrical appliances manufacture, Furniture manufacture spraying, packages printing, Electronic products manufacturing, leather add Work, cables manufacturing, Pesticide use etc..

System for reclaiming VOC

On the other hand, the application provides a kind of system for reclaiming VOC.The system can wrap Condensing unit and absorbing unit are included to handle the fluid for including VOCs, wherein the condensing unit can be with the absorbing unit fluid Connection.The condensing unit can be included and waved using the condensing unit and the liquid low temperature cooling medium of liquid low temperature cooling medium Hair produces inert gas.The inert gas can be in fluid communication with the absorbing unit and at least a portion of the inert gas Can be used for the regeneration of sorbing material in the absorbing unit, and/or the inert gas can with it is pending described in include Be in fluid communication between VOCs fluid and at least a portion of the inert gas can with it is pending described in include VOCs fluid Mix to adjust oxygen content therein.In some embodiments, the oxygen content in the pending fluid comprising VOCs It is adjusted to less than the safety limit of oxygen or outside the explosion limit of oxygen.For example, in the mixed gas comprising methane, oxygen Safety limit can be no more than about 15%, no more than about 14%, no more than about 13%, no more than about 12%, no more than about 11.5%, no more than about 11%, no more than about 10.5%, no more than about 10%, no more than about 9.5%, no more than about 9%, no Greater than about 8%, no more than about 7%, no more than about 6%, no more than about 5%, no more than about 4%, no more than about 3%, are not higher than About 2%, no more than about 1%, no more than about 0.5% or lower.For example, can be by adjusting inert gas in the mixed gas Content and cause the oxygen content in the pending fluid comprising VOCs to be not higher than safety limit or in the blast pole of oxygen Outside limit.

In some embodiments, the condensing unit is provided so that the pending bag with the absorbing unit Fluid containing VOCs is subjected to the adsorption treatment before the condensation process.For example, the pending fluid comprising VOCs can Absorbing unit processing is initially subjected to be introduced into absorbing unit, the absorbing unit processing produces unadsorbed fluid, unadsorbed fluid Absorption tail gas can be used as, adsorbed part can be desorbed to obtain the stream for including VOCs after absorbing unit is handled Body, the absorbing unit can be in fluid communication with condensing unit, and the fluid comprising VOCs after absorbing unit is handled can enter One step is introduced into condensing unit and carries out and be subjected to condensing unit processing, and can be handled by condensing unit and obtain VOCs condensate liquids And/or fluid is not coagulated, at least a portion of the not solidifying fluid after condensed cell processing can include VOCs's with pending Fluid mixes and/or is re-introduced into absorbing unit and carries out adsorption treatment.

In some embodiments, the condensing unit is provided so that at through the condensation with the absorbing unit After reason, obtained not solidifying fluid is handled through the absorbing unit.For example, the pending fluid comprising VOCs can be by Introduce condensing unit and carry out condensation process, and VOCs condensate liquids can be obtained and/or do not coagulate fluid, the condensing unit can be with Absorbing unit is in fluid communication, and the not solidifying fluid after condensed cell processing can be further introduced into absorbing unit and carry out at absorption Reason, unadsorbed fluid can be used as absorption tail gas.

The condensing unit can include wall-type heat exchange device, fluidly connect indirect type heat-exchanger rig etc..The partition Formula heat-exchanger rig can be such as shell-and-tube cooler, tube-in-tube condenser；It is described fluidly connect indirect type heat-exchanger rig can To be such as evaporative condenser.The heat exchanger can be, such as coil exchanger, tubular heat exchanger are (such as two-tube Heat exchanger), plate-fin heat exchanger, accumulation of heat material filling type heat exchanger or filler (column plate) formula heat exchanger.The condensing unit can be with Including multi-stage condensing device, for example, precondenser, one or more condensers (such as first-stage condenser, secondary condenser) etc..Institute Stating can be in fluid communication between multi-stage condensing device successively, for example, the precondenser can be in fluid communication with first-stage condenser, institute Stating first-stage condenser can be in fluid communication with secondary condenser.The condensing unit is provided so as to treat with the absorbing unit The fluid comprising VOCs of processing is before the condensation process when being subjected to the adsorption treatment, and the in multi-stage condensing device First-stage condenser and/or afterbody condenser can be in fluid communication with the adsorbent equipment in absorbing unit.It is for example, pending Fluid comprising VOCs can be introduced into absorbing unit and carry out adsorption treatment, and adsorbed part can be desorbed to obtain through inhaling The fluid for including VOCs after attached processing, it is cold that the fluid comprising VOCs after adsorption treatment can be introduced into precondenser progress Solidifying processing, the not solidifying fluid of preliminary condensation and/or preliminary condensation VOCs condensate liquids are obtained, it is cold that the not solidifying fluid of preliminary condensation can be introduced into one-level Condenser carries out condensation process, obtains the not solidifying fluid of one-level condensation and/or fluid is not coagulated in one-level condensation VOCs condensate liquids, one-level condensation Secondary condenser can be introduced into and carry out condensation process, obtain the not solidifying fluid of B-grade condensation and/or B-grade condensation VOCs condensate liquids, Condensation VOCs condensate liquids at different levels can be incorporated as VOCs condensate liquids.In some embodiments, handled through secondary condenser Caused not solidifying fluid can be introduced into absorbing unit progress adsorption treatment after pre-cooled condenser processing heating afterwards.The condensing unit With the absorbing unit be provided so that it is pending described in comprising VOCs fluid institute is subjected to after the condensation process When stating adsorption treatment, the afterbody condenser in multi-stage condensing device can be in fluid communication with the adsorbent equipment in absorbing unit, For example, the pending fluid comprising VOCs, which can be introduced into precondenser, carries out condensation process, obtain preliminary condensation and do not coagulate fluid And/or preliminary condensation VOCs condensate liquids, the not solidifying fluid of preliminary condensation can be introduced into first-stage condenser and carry out condensation process, obtain one-level The not solidifying fluid of condensation and/or one-level condensation VOCs condensate liquids, the not solidifying fluid of one-level condensation can be introduced into secondary condenser progress Condensation process, obtains the not solidifying fluid of B-grade condensation and/or B-grade condensation VOCs condensate liquids, and condensation VOCs condensate liquids at different levels can be by Merge.Not solidifying fluid caused by after secondary condenser is handled can be introduced into absorbing unit progress after pre-cooled condenser processing heating Adsorption treatment.Therefore, the condensing unit may also include following one or more assemblies：Cryogenic condensation medium (such as liquid nitrogen) Storage tank, cryogenic condensation medium pump, precondenser, first-stage condenser, secondary condenser, cooling medium evaporator, inert gas storage Tank, oil water separator, layering groove, vavuum pump and blower fan etc..In some embodiments, the condensing unit can also include control Unit processed, described control unit can regulate and control one or more assemblies in the condensing unit.For example, in some embodiments In, described control unit can cause multiple condenser alternations in the condensing unit.For example, described control unit can To cause one or more of condensing unit condenser working, and cause other condensations in the condensing unit simultaneously Device is stopped.

In the condensing unit processing procedure, the cryogenic condensation medium, which can produce, can make the liquefied low temperature of VOCs, Pass through the heat exchange between the fluid comprising VOCs and cryogenic condensation medium so that the VOCs component liquid in the fluid comprising VOCs Change, so as to obtain VOCs condensate liquids, and cryogenic condensation medium can volatilize and produce inert gas.The condensation process can also produce Raw not coagulate fluid, the not solidifying fluid can be further subjected to adsorption treatment.Those skilled in the art can according to VOCs species, It is determined to make the liquefied low temperature of VOCs.It is not intended to be bound by theory, however, for same VOC components, with partial pressure Reduce, its condensing temperature can be reduced correspondingly.For example, at normal atmospheric pressure, the low temperature that dichloromethane liquefies can be made for not Temperature higher than 39.8 DEG C；At normal atmospheric pressure, the liquefied low temperature of toluene can be made for the temperature not higher than 110.6 DEG C. The cryogenic condensation medium that can be used in condensation process includes but is not limited to, such as liquid nitrogen, liquid helium, and/or liquid carbon dioxide And their mixture.The inert gas that can be obtained in condensation process includes but is not limited to, such as nitrogen, argon gas, two Carbonoxide and their mixture.The inert gas is generally the gas form of cryogenic condensation medium, for example, working as low temperature cold When solidifying medium can be liquid nitrogen, inert gas can be then nitrogen.

In the system of the application, the cryogenic temperature of the cryogenic condensation medium can be, such as -70 DEG C to -160 DEG C, Such as less than -70 DEG C, less than -80 DEG C, less than -90 DEG C, less than -100 DEG C, less than -110 DEG C, less than -120 DEG C, -130 DEG C with Under, less than -140 DEG C, less than -150 DEG C, or -160 DEG C such as the following.In some embodiments, the system of the cryogenic condensation medium Cold temperature can be, such as -90 DEG C to -160 DEG C, -95 DEG C to -160 DEG C, -100 DEG C to -160 DEG C, -105 DEG C to -160 DEG C, - 110 DEG C to -160 DEG C, -120 DEG C to -160 DEG C, -130 DEG C to -160 DEG C, -140 DEG C to -160 DEG C, -150 DEG C to -160 DEG C etc..

The absorbing unit includes adsorbent equipment, and the adsorbent equipment can include, such as pressure-swing absorption apparatus, alternating temperature are inhaled Adsorption device and/or alternating temperature pressure-swing absorption apparatus etc..In adsorbent equipment, the adsorbent that can be used includes but is not limited to, such as Activated carbon, carbon molecular sieve, natural zeolite, modified zeolite (such as sial based molecular sieve), mesopore molecular sieve, titanium-based molecular sieve, gold Belong to organic framework materials and their mixture.In some embodiments, the adsorbent does not include NACF. In some embodiments, the adsorbent includes activated carbon granule.In some embodiments, the adsorbent includes molecule Sieve.In the absorbing unit processing, for example, VOCs fluid can be included under conditions of low temperature, high pressure using adsorbent absorption Middle VOCs components, unadsorbed part can be unadsorbed fluids, and can be desorbed in the case of high temperature and/or low pressure with reality The regeneration of existing sorbing material.At least one of the stripping gas obtained in the application some embodiments, during regneration of adsorbent material Condensation process can be further subjected to by dividing, to obtain VOCs condensate liquids.

The renovation process of sorbing material can be the method for separating adsorbed material and adsorbent, for example, heating, drop The methods of pressing, being purged using gas.In the application some embodiments, renovation process can be inhaled using regeneration gas purging Attached adsorbent on the adsorbent material, the regeneration gas can include indifferent gas caused by the volatilization of liquid low temperature cooling medium At least a portion of body, the inert gas of external source can also be included, such as may include but be not limited to：Nitrogen, carbon dioxide, argon gas Or air etc., or their any combination.In some embodiments of the application, the regeneration gas can include described At least a portion of unadsorbed fluid (for example, absorption tail gas).

In some embodiments, the system also includes oxygen probe, and the oxygen probe be used to make pending institute State the fluid comprising VOCs to handle with before condensing unit processing through absorbing unit, detect the pending stream for including VOCs Oxygen content in body.After the oxygen content in obtaining the pending fluid comprising VOCs, the indifferent gas can be passed through At least a portion of body adjusts the oxygen content in the pending fluid comprising VOCs.The oxygen probe can be such as oxygen Change zirconium oxygen probe, titanium oxide oxygen probe etc..The zirconium oxide-oxygen probe is typically to make solid dielectric with zirconium oxide, is situated between using electricity Oxygen concentration cell is formed during the oxygen concentration difference of matter both sides, to determine oxygen content；Titanium oxide oxygen probe is typically to utilize titanium dioxide Device made of the characteristic that the resistance value of material changes with the change of oxygen content in exhaust.

The system can also include collector unit, and the collector unit can be used for collecting the pending stream for including VOCs Inert gas caused by unadsorbed fluid and/or condensing unit caused by body and/or absorbing unit.For example, the oxygen probe can To be connected with collector unit signal, the collector unit can be in fluid communication with absorbing unit and/or condensing unit, the collection Unit collects the pending fluid for including VOCs, and can be obtained by the oxygen probe in pending VOCs fluid Oxygen content.The system of the application can according to the oxygen content measured come adjust be passed through it is described unadsorbed in the collector unit The amount of fluid and/or the inert gas, so as to adjust the oxygen content in the pending fluid comprising VOCs.

In some embodiments, the system also includes compression unit, and the compression unit is arranged in detection institute After stating oxygen content, and make it is pending described in before the fluid comprising VOCs enters the absorbing unit and condensing unit, Fluid comprising VOCs described in pending is compressed.The compression unit can include compression set, such as can be Low-pressure gas is promoted to device of gases at high pressure etc..The compression set can be, for example, centrifugal gas compressor, Reciprocating compression set, injecting type compression set, screw-compression device etc..The centrifugal gas compressor be typically by Impeller drives gas to do rotation at a high speed, gas is produced centrifugal force, due to diffusion flowing of the gas in impeller, so that gas It is improved by the flow velocity after impeller and pressure, continuously produces the device of compressed gas；The reciprocating compression set Typically using compressing reciprocating motion of the original paper (for example, piston) in cylinder, and by the automatic shutter of inlet and outlet valve, make Enter cylinder working chamber, the device for being compressed and discharging gases cycle；The injecting type compression set is typically to utilize High-speed gas injection stream takes away the gas of suction, then the speed of mixed gas is converted into the device of pressure on diffuser； The screw-compression device is typically to utilize two rotors with screw type gear in device to be intermeshed, so as to by gas The device for compressing and discharging.

The compression unit can be in fluid communication with absorbing unit or condensing unit, for example, when making pending to include VOCs Fluid when first introducing condensing unit, compression unit is in fluid communication with condensing unit；When by the pending fluid for including VOCs When first introducing absorbing unit, compression unit is in fluid communication with absorbing unit.The compression unit can also be with collector unit fluid Connection.In some embodiments, the pending fluid comprising VOCs can be made to be initially subjected to condensation process.In the condensation Before processing, and (by using the indifferent gas after the oxygen content in have detected the pending fluid comprising VOCs Body is adjusted, and the oxygen content is adjusted to the safety limit less than oxygen), can be by the pending stream for including VOCs It is not less than about 0.01MPa, not less than about not less than about 0.05MPa, 0.1MPa that body is compressed to its pressure through the compression unit, Not less than about 0.15MPa, not less than about 0.2MPa, not less than about 0.25MPa, not less than about 0.3MPa, not less than about 0.4MPa, Not less than about 0.5MPa, not less than about 0.6MPa, not less than about 0.8MPa, or not less than about 1.0MPa.For example, in some implementations In mode, the compression unit can realize one stage of compression or two stages of compression.In some embodiments, make through the compression unit Compression ratio after is for example, no more than 3, no more than 2.5, no more than 2, or no more than 1.5.

In some embodiments, the system includes compression unit, the compression unit be arranged to make it is pending The fluid comprising VOCs enter the absorbing unit and condensing unit before do not detect oxygen content and to pending institute The fluid comprising VOCs is stated to be compressed (for example, when the oxygen content in the pending fluid comprising VOCs is substantially in oxygen Safety limit in the range of or when outside the explosion limit of oxygen).

In some embodiments, the absorbing unit produces unadsorbed fluid, the unadsorbed fluid can with it is pending The fluid comprising VOCs between be in fluid communication and at least a portion of the unadsorbed fluid can be with the pending bag Fluid containing VOCs is mixed to adjust oxygen content therein, and/or the unadsorbed fluid can connect with the absorbing unit fluid At least a portion of logical and described unadsorbed fluid can be used for the regeneration of sorbing material in the absorbing unit.The system is also Collector unit can be included, the collector unit can be used for collecting the pending fluid comprising VOCs and/or absorbing unit production Inert gas caused by raw unadsorbed fluid and/or condensing unit.The collector unit can be in fluid communication with absorbing unit, The collector unit collects the pending fluid for including VOCs, and can obtain pending include by the oxygen probe Oxygen content in VOCs fluid, can according to the oxygen content measured come adjust be passed through in the collector unit described in do not inhale The amount of attached fluid, so as to adjust the oxygen content in the pending fluid comprising VOCs.

The system can also include inert gas storage unit, the inert gas storage unit and condensing unit fluid Connection, the inert gas storage unit include nitrogen storage device.The liquid low temperature cooling medium volatilization produces indifferent gas Body is used directly for subsequent step, can also be stored in inert gas storage unit and use when needed.The inertia Gas storage units include inert gas storage device, the inert gas storage device can be suitable for nitrogen storage and/ Or the gas storage device received, it may include metal tank, nonmetallic storage tank and metal and nonmetal composite storage tank etc..

In some embodiments, the absorbing unit may include：It is adsorption beds of the one or more comprising adsorbent, true Sky solution sucking pump, heater, blower fan, cooler etc., they are in fluid communication with each other.The desorption process of the absorbing unit may include profit Desorbed with Vacuum solutions sucking pump and purged using regeneration gas.For example, the desorption process may include：First pass through Vacuum solutions Sucking pump vacuumizes a period of time to the adsorption bed (for example, more than 0.1 minute, more than 1 minute, more than 5 minutes, 10 minutes More than, more than 15 minutes, more than 20 minutes, more than 25 minutes, more than 30 minutes, more than 35 minutes, more than 40 minutes, 45 minutes More than, more than 50 minutes, such as 5-50 minutes, 10-40 minutes, 15-30 minutes etc.), regeneration is subsequently or simultaneously blowed by blower fan Gas (for example, the inert gas through volatilization, such as nitrogen) is to be purged；Then with the institute heated through the heater Regeneration gas (for example, the inert gas through volatilization, such as nitrogen) is stated to be purged (for example, pulsed purging)；Afterwards With the regeneration gas (for example, the inert gas through volatilization, such as nitrogen) the cooling absorbing unit (for example, absorption Bed).When being purged with the heated regeneration gas (for example, pulsed purging), the regeneration gas of the heating Inlet temperature can be not less than about 90 degrees Celsius, not less than about 95 degrees Celsius, not less than about 100 degrees Celsius, not less than about 105 degrees Celsius, not less than about 110 degrees Celsius, not less than about 115 degrees Celsius, not less than about 120 degrees Celsius, taken the photograph not less than about 125 Family name's degree, not less than about 130 degrees Celsius, not less than about 135 degrees Celsius, not less than about 140 degrees Celsius, not less than about 150 degrees Celsius, It is not low not less than about 190 degrees Celsius not less than about 180 degrees Celsius not less than about 170 degrees Celsius not less than about 160 degrees Celsius In about 200 degrees Celsius, not less than about 210 degrees Celsius, or not less than about 220 degrees Celsius.For example, the regeneration gas of the heating Inlet temperature can be about about 145 degrees Celsius of 95- or about 140 degrees Celsius of about 100-.When Outlet Gas Temperature reaches for example not high In 60 degrees Celsius (for example, not higher than 55 degrees Celsius, not higher than 50 degrees Celsius, not higher than 45 degrees Celsius, not higher than 40 degrees Celsius, Or not higher than 35 degrees Celsius) when can stop the entrance of regeneration gas heated described in entrance, and start to the adsorption system Cooled down.In some embodiments, in the desorption process, before by vacuum desorption pumping vacuum, can first use The regeneration gas (for example, the inert gas through volatilization, such as nitrogen) purging a period of time (for example, more than 2 minutes, 5 More than minute, more than 10 minutes, more than 15 minutes, more than 20 minutes, more than 25 minutes, more than 30 minutes, such as 2-30 minutes, 5- 30 minutes, 5-20 minutes, 10-20 minutes etc.).The adsorption treatment process of the application, which greatly reduces energy consumption and improved, is The operating efficiency of system.

The system of the application can be used for petroleum vapor recovery or the part as gas recovery system for oil.The system of the application The VOCs recovery that can be additionally used in during following one or more：Oil refining production, petrochemicals production, organic chemistry raw material Produce (such as solvent production), medicinal chemicals production, oil depot accumulating, oil tank accumulating, chemicals storage, chemicals transhipment, change Product dispatching, paint production and use, building coating production and use, Printing ink producing and use, Polymer Synthesizing, food production And use, commodity production and use, pesticide producing and use, Feed Manufacturing and use, Tire production, fuel combustion, steel Smelting, textile printing and dyeing, papermaking, automobile making, shipbuilding, aircraft manufacturing, household electrical appliances manufacture, Furniture manufacture spraying, packages printing, Electronic products manufacturing, leather processing, cables manufacturing, Pesticide use etc..In this application, described " petroleum vapor recovery " typically refers to back Receive oil product (such as gasoline) in accumulating, cargo handling process (for example, handling gasoline or to group refueling during) volatilization or The process or method of the oil gas discharged otherwise.

The gas recovery system for oil effect of oil truck is during road tanker loading, realizes totally-enclosed gas recovery, limitation Oil gas discharges into air.It is to connect into a closed oil gas in the petroleum pipeline and gas collection pipe of oil truck and oil storage tank and return Closed tube road.While oil truck is by unloading line emptying, the oil gas in gas station's oil tank returns to oil truck by return line In.Oil gas is taken back oil depot and handled by oil truck, reaches the purpose of petroleum vapor recovery.Oil product can rise and fall when inputting because liquid level shakes And increase the volatilization and loss of oil gas, therefore oil fuel tube must go deep into below pasta, to reduce liquid surface fluctuation.Gas collection pipe is opened It is that device has special opening function device at mouthful, when the petroleum vapor recovery pipeline of oil truck is correctly connected to oil groove, reclaims eloquence It can open, while blast pipe is closed, enable the oil gas of oil groove completely by recovery port oil return tank car.

For example, gas recovery system for oil can be made up of three parts：The snap joint of pot bottom and cap, manual or pneumatic operated valve, Elbow, seamless steel pipe；Through tank base and the seamless steel pipe at top, or exterior line connection system；The elbow of tank top, hand Dynamic or pneumatic operated valve, sebific duct, parallel connection are responsible for, and return the elbow etc. in tank body.

Fig. 1 shows that the application is used for an example for reclaiming the system of VOC.The system includes receiving Collect unit 101, the collector unit 101 is used to collect the pending fluid 121 comprising VOCs (in some embodiments, The collector unit 101 is additionally operable to collect unadsorbed fluid 131 or absorption tail gas 133 caused by absorbing unit 102 and/or condensation Inert gas 127 caused by unit), and treated by the regulation of unadsorbed fluid 131, absorption tail gas 133 and/or inert gas 127 Oxygen content in the gas 121 of processing.Collector unit 101 is in fluid communication with compression unit 112, from the adjusted of collector unit Gas 122 can be introduced into compression unit 112 and be compressed, and generate compressed gas 123.Condensing unit 108 respectively with Compression unit 112, cryogenic condensation dielectric memory cell 109 are in fluid communication, the gas 123 and cryogenic condensation media storage list of compression Cryogenic condensation medium 129 in member 109 is introduced into condensing unit 108 and carries out heat exchange, and the cryogenic condensation medium 129 after gasification is given birth to Into inert gas 125, the compressed part of gas 123, which is condensed to liquefy, generates VOCs condensate liquids 130, not liquefied part life Cheng Buning fluids 124.The condensing unit 108 and inert gas storage unit 111, VOC condensate tanks 110 and absorbing unit 102 are in fluid communication, and the VOCs condensate liquids 130 are collected in VOC condensate tanks 110, and the inert gas 125 is collected In inert gas storage unit 111, the not solidifying fluid 124 is introduced into absorbing unit 102 and through being inhaled in absorbing unit 102 Unadsorbed fluid 131 is generated after receiving unit 102B processing, the absorbing unit 102 is in fluid communication with collector unit 101, unadsorbed Fluid 131 and/or absorption tail gas 133 can be introduced into collector unit 101, described pending comprising VOCs for adjusting Oxygen content in fluid 121；The absorbing unit 102 can be also in fluid communication by air exhaust units 106 and exhaust unit 107, not Fluid-absorbent 131 can also generate the gas 132 handled through air exhaust units by air exhaust units 106, be handled through air exhaust units Gas 132 is further introduced into exhaust unit 107 and discharged as absorption tail gas 133.The inert gas storage unit 111 can be in fluid communication with inert gas storage unit 113 and inert gas storage unit 105, and one in the inert gas 125 Part inert gas 127 is introduced into inert gas storage unit 113, and a part of inert gas 126 is introduced into inert gas storage Unit 105.Inert gas storage unit 113 is in fluid communication with collector unit 101, the inertia in inert gas storage unit 113 Gas 128, which can be introduced into collector unit 101, to be used to adjust the oxygen content in the pending fluid 121 comprising VOCs. Inert gas storage unit 105 can be in fluid communication with removing blower fan 104, the indifferent gas in the inert gas storage unit 105 Body 134 can be introduced into removing blower fan 104 and be blowed and/or compressed by the removing blower fan 104.The removing blower fan 104 can be with Absorbing unit 102 is in fluid communication, and may be heated after unit 103 heats and is passed through through the inert gas 135 of removing blower fan processing The inert gas 136 of heating, heated inert gas 136 can be further introduced into the desorption unit in absorbing unit 102 102A is used for the regeneration of sorbing material.

Fig. 2 shows that the application is used for another example for reclaiming the system of VOC.The system includes receiving Collect unit 201, the collector unit 201 is used to collect the pending fluid 221 comprising VOCs (in some embodiments, The collector unit 201 is additionally operable to collect unadsorbed fluid 231 or absorption tail gas 233 caused by absorbing unit 202 and/or condensation Inert gas 227 caused by unit), and adjusted by unadsorbed fluid 231, absorption tail gas 233 and/or inert gas 227 Oxygen content in pending gas 221.Collector unit 201 can be in fluid communication with compression unit 212, the warp from collector unit The gas 222 of regulation can be introduced into compression unit 212 and be compressed, and generate compressed gas 223.The absorbing unit 202 are in fluid communication with compression unit 212, and the gas 223 of the compression after the compressed processing of unit 212 is introduced into absorbing unit 202 In, and absorptive unit 202B processing in absorbing unit 202 is subjected to, unadsorbed fluid 231 is generated, the absorbing unit 202 can lead to Cross desorption unit 202A therein and generate the fluid 224 (stripping gas) comprising VOCs after absorbing unit is handled.In some realities Apply in mode, the adjusted gas 222 can not be compressed and be introduced directly into absorbing unit 202 and be subjected at absorption Reason.The absorbing unit 202 is in fluid communication with collector unit 201, and unadsorbed fluid 231 or absorption tail gas 233 can be introduced into In collector unit 201, for adjusting the oxygen content in the pending fluid 221 comprising VOCs；The absorbing unit 202 It can be also in fluid communication by air exhaust units 206 and exhaust unit 207, unadsorbed fluid 231 can also be given birth to by air exhaust units 206 Into the gas 232 handled through air exhaust units, the gas 232 handled through air exhaust units is further introduced into exhaust unit 207 and made Discharged for absorption tail gas 233.The condensing unit 208 respectively with absorbing unit 202, cryogenic condensation dielectric memory cell 209 are in fluid communication, and it is single that the fluid 224 comprising VOCs and cryogenic condensation medium 229 after absorbing unit is handled are introduced into condensation Member 208 carries out heat exchange, and the cryogenic condensation medium 229 after gasification generates inert gas 225, including after absorbing unit is handled The VOCs part of fluid 224, which is liquefied, generates VOCs condensate liquids 230, and fluid 237 is not coagulated in not liquefied part generation, not solidifying stream Body 237 is further introduced into absorbing unit 202 and is subjected to adsorption treatment.Condensing unit 208 respectively with VOC condensate tanks 210 and Inert gas storage unit 211 is in fluid communication.The VOC condensate liquids 230 are collected in VOC condensate tanks 210；It is described lazy Property gas 225 is collected in inert gas storage unit 211.The inert gas storage unit 211 and inert gas storage Unit 213 and inert gas storage unit 205 are in fluid communication, and a part of inert gas 227 in the inert gas 225 is drawn Enter inert gas storage unit 213, a part of inert gas 226 is introduced into inert gas storage unit 205.Inert gas storage Unit 213 is in fluid communication with collector unit 201, and it is single that the inert gas 228 in inert gas storage unit 213 can be introduced into collection Member 201 is used to adjust the oxygen content in the pending fluid 221 comprising VOCs.Inert gas storage unit 205 can be with Removing blower fan 204 is in fluid communication, and the inert gas 234 in the inert gas storage unit 205 can be introduced into removing blower fan 204 And be blown from and/or compress, generate the inert gas 235 through removing blower fan processing.The removing blower fan 204 and absorbing unit 202 are in fluid communication, and heated inertia is obtained after the heating of heating unit 203 through the inert gas 235 of removing blower fan processing Gas 236, the desorption unit 202A that heated inert gas 236 can be further introduced into absorbing unit 202 are used to adsorb The regeneration of material, and generate the fluid 224 comprising VOCs after absorbing unit is handled.

The application further relates to following detailed description：

1st, a kind of method for being used to reclaim VOC (VOCs), methods described include：Make pending bag Fluid containing VOCs obtains VOCs condensate liquids through adsorption treatment and condensation process, wherein the condensation is condensed using liquid low temperature Medium, the liquid low temperature cooling medium volatilization produces inert gas, and at least a portion of the inert gas is used for institute State sorbing material in absorption regeneration and/or the regulation pending fluid comprising VOCs in oxygen content.

2nd, the method according to embodiment 1, wherein the liquid low temperature cooling medium is liquid nitrogen.

3rd, the method according to any one of embodiment 1-2, wherein the inert gas is nitrogen.

4th, the method according to any one of embodiment 1-3, wherein before the condensation process, make described to wait to locate The fluid comprising VOCs of reason is subjected to the adsorption treatment.

5th, the method according to any one of embodiment 1-4, wherein after the condensation process, so as to get Not solidifying fluid is subjected to the adsorption treatment.

6th, the method according to any one of embodiment 1-5, wherein making the pending stream for including VOCs Before body is through adsorption treatment and condensation process, the oxygen content in the pending fluid comprising VOCs is detected.

7th, the method according to embodiment 6, wherein after the oxygen content is detected, and make it is described pending Before fluid comprising VOCs is through the adsorption treatment and condensation process, the pending fluid comprising VOCs is pressed Contracting.

8th, the method according to any one of embodiment 1-5, wherein making the pending stream for including VOCs Before body is through the adsorption treatment and condensation process, the pending fluid comprising VOCs is compressed.

9th, the method according to any one of embodiment 1-8, wherein the adsorption treatment including the use of pressure-variable adsorption, Temp.-changing adsorption and/or pressure and temperature varying absorption.

10th, the method according to any one of embodiment 1-9, wherein the adsorption treatment produces unadsorbed fluid, At least a portion of the unadsorbed fluid is used for the regeneration of sorbing material in the absorption and/or adjusted described pending Oxygen content in fluid comprising VOCs.

11st, the method according to any one of embodiment 1-10, wherein methods described are used for petroleum vapor recovery.

12nd, a kind of system for being used to reclaim VOC (VOCs), the system include condensing unit and suction Coupon member includes VOCs fluid to handle, wherein the condensing unit is in fluid communication with the absorbing unit, the condensation is single Member includes produces inert gas using the condensing unit of liquid low temperature cooling medium and liquid low temperature cooling medium volatilization, its Described in inert gas and the absorbing unit be in fluid communication and at least a portion of the inert gas is used for the absorption It is in fluid communication between the regeneration of sorbing material in unit, and/or the inert gas and the pending fluid comprising VOCs And at least a portion of the inert gas with it is pending described in mix to adjust oxygen content therein comprising VOCs fluid.

13rd, the system according to embodiment 12, wherein the liquid low temperature cooling medium is liquid nitrogen.

14th, the system according to any one of embodiment 12-13, wherein the inert gas is nitrogen.

15th, the system according to any one of embodiment 12-14, wherein the condensing unit and the absorbing unit It is provided so that the pending fluid comprising VOCs before being handled through the condensing unit through the absorbing unit Processing.

16th, the system according to any one of embodiment 12-15, wherein the condensing unit and the absorbing unit It is provided so that after being handled through the condensing unit, obtained not solidifying fluid is handled through the absorbing unit.

17th, the system according to any one of embodiment 12-16, it also includes oxygen probe, the oxygen probe by with In make it is pending described in the fluid comprising VOCs through adsorption treatment and condensation process before, detect pending described include Oxygen content in VOCs fluid.

18th, the system according to embodiment 17, it also includes compression unit, and the compression unit is arranged to examining Survey after the oxygen content, and make it is pending described in the fluid comprising VOCs enter the absorbing unit and condensing unit it Before, the fluid comprising VOCs described in pending is compressed.

19th, the system according to any one of embodiment 12-16, it also includes compression unit, the compression unit Be arranged to make it is pending described in before the fluid comprising VOCs enters the absorbing unit and condensing unit, to pending The fluid comprising VOCs be compressed.

20th, the system according to any one of embodiment 12-19, wherein the absorbing unit includes pressure-variable adsorption list Member, temperature swing adsorption unit, and/or pressure and temperature varying absorbing unit.

21st, the system according to any one of embodiment 12-20, wherein the absorbing unit produces unadsorbed stream Body, between the unadsorbed fluid and the pending fluid comprising VOCs be in fluid communication and the unadsorbed fluid at least It is a part of to be mixed with the pending fluid comprising VOCs to adjust oxygen content therein, and/or the unadsorbed fluid It is in fluid communication with the absorbing unit and at least a portion of the unadsorbed fluid is used for adsorption material in the absorbing unit The regeneration of material.

22nd, the system according to any one of embodiment 12-21, wherein the condensing unit includes following one Or multiple components：Precondenser, one or more condensers, storage tank, oil water separator, pump, blower fan and compressor.

23rd, the system according to any one of embodiment 12-22, it is used for petroleum vapor recovery either petroleum vapor recovery system The part of system.

Embodiment

The present processes of embodiment 1 and system are used for petroleum vapor recovery

In this embodiment, petroleum vapor recovery is carried out by the system shown in Fig. 1.

Sample oil tank is sampled under 35 degrees Celsius, and analyzes the content of wherein oil gas composition, the results are shown in Table 1.Through Detection, the concentration of porch NMHC quality is 798.8g/m³。

The sample gas of oil storage tank component of table 1 (35 DEG C of probe temperature)

The treating capacity of oil gas is set to 100m³/ hr, the analog result after the system and method processing of the application is in table 2 Shown into table 4.

The corresponding relation (1 absolute atmosphere) of the condensation temperature of table 2 and the NMHC rate of recovery

Condensation temperature (DEG C)	The rate of recovery	Tail gas VOCs concentration (g/m³)
			-40	64.7	218.7
-70	92.1	62.0
			-95	97.9	17.52
-110	99.1	7.91
			-130	99.8	1.9
-140	99.9	0.72
			-150	99.9	0.22

The corresponding relation (3 absolute atmospheres) of the condensation temperature of table 3 and the NMHC rate of recovery

Condensation temperature (DEG C)	The rate of recovery	Tail gas VOCs concentration (g/m³)
			-40	85.8	105.1
-70	96.5	28.7
			-95	99.0	8.41
-110	99.6	3.46
			-130	99.9	0.71
-140	99.9	0.26
			-150	99.9	0.08

The corresponding relation (5 absolute atmospheres) of the condensation temperature of table 4 and the NMHC rate of recovery

Condensation temperature (DEG C)	The rate of recovery	Tail gas VOCs concentration (g/m³)
			-40	90.6	72.9
-70	97.6	20.3
			-95	99.3	5.8
-110	99.7	2.3
			-130	99.9	0.46
-140	99.9	0.17
			-150	99.9	0.05

From result above, at the same pressure, with the decline of condensation temperature, oil gas recovery rate rises, while tail Gas VOCs concentration drastically declines.In addition, by the system and method for the application, appropriate compression pressure, cryogenic condensation temperature are utilized Spend and adsorb to carry out petroleum vapor recovery, reduce the total energy consumption of system so that oil gas recovery rate greatly improves, and VOCs in tail gas Concentration be greatly reduced.

Foregoing detailed description is to be provided with explaining with way of example, is not intended to limit scope of the following claims. A variety of changes of illustrated embodiments set forth herein at present are it will be apparent that and retaining for those of ordinary skills In the range of appended claim and its equivalent.

Claims

1. one kind is used for the method for reclaiming VOC (VOCs), methods described includes：Make pending include VOCs fluid obtains VOCs condensate liquids through adsorption treatment and condensation process, wherein the condensation is situated between using liquid low temperature condensation Matter, the liquid low temperature cooling medium volatilization generation inert gas, and at least a portion of the inert gas are used for described Oxygen content in absorption in the regeneration of sorbing material and/or the regulation pending fluid comprising VOCs.

2. according to the method for claim 1, wherein the liquid low temperature cooling medium is liquid nitrogen.

3. according to the method any one of claim 1-2, wherein the inert gas is nitrogen.

4. according to the method any one of claim 1-3, wherein before the condensation process, make described pending Fluid comprising VOCs is subjected to the adsorption treatment.

5. according to the method any one of claim 1-4, wherein after the condensation process, so as to get do not coagulate Fluid is subjected to the adsorption treatment.

6. one kind is used for the system for reclaiming VOC (VOCs), the system includes condensing unit and absorbing unit VOCs fluid is included with processing, wherein the condensing unit is in fluid communication with the absorbing unit, the condensing unit includes Inert gas is produced using the condensing unit of liquid low temperature cooling medium and liquid low temperature cooling medium volatilization, wherein described Inert gas is in fluid communication with the absorbing unit and at least a portion of the inert gas is used in the absorbing unit It is in fluid communication between the regeneration of sorbing material, and/or the inert gas and the pending fluid comprising VOCs and described At least a portion of inert gas with it is pending described in mix to adjust oxygen content therein comprising VOCs fluid.

7. system according to claim 6, wherein the liquid low temperature cooling medium is liquid nitrogen.

8. according to the system any one of claim 6-7, wherein the inert gas is nitrogen.

9. according to the system any one of claim 6-8, wherein the condensing unit is set with the absorbing unit For cause it is pending described in comprising VOCs fluid through the condensing unit handle before through the absorbing unit handle.

10. according to the system any one of claim 6-9, wherein the condensing unit is set with the absorbing unit To cause after being handled through the condensing unit, obtained not solidifying fluid is handled through the absorbing unit.