WO2019165834A1 - 处理氯铝酸类离子液体废催化剂和碱性废水的方法和系统 - Google Patents

处理氯铝酸类离子液体废催化剂和碱性废水的方法和系统 Download PDF

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WO2019165834A1
WO2019165834A1 PCT/CN2018/123215 CN2018123215W WO2019165834A1 WO 2019165834 A1 WO2019165834 A1 WO 2019165834A1 CN 2018123215 W CN2018123215 W CN 2018123215W WO 2019165834 A1 WO2019165834 A1 WO 2019165834A1
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water
reactor
spent catalyst
neutralization
hydrolysis
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PCT/CN2018/123215
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English (en)
French (fr)
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陈春茂
刘植昌
易忠进
张睿
梁家豪
孟祥海
刘海燕
徐春明
王庆宏
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中国石油大学(北京)
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Priority to CA3092413A priority Critical patent/CA3092413C/en
Priority to CN201880090315.6A priority patent/CN111770791B/zh
Publication of WO2019165834A1 publication Critical patent/WO2019165834A1/zh
Priority to US17/006,723 priority patent/US11426702B2/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • B01J4/004—Sparger-type elements
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/13—Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B5/00—Treatment of  metallurgical  slag ; Artificial stone from molten  metallurgical  slag 
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5281—Installations for water purification using chemical agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
    • C02F11/127—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering by centrifugation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/16—Treatment of sludge; Devices therefor by de-watering, drying or thickening using drying or composting beds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • C10G2300/701—Use of spent catalysts

Definitions

  • the invention belongs to the technical field of petrochemical industry, and particularly relates to a method and a system for treating a waste catalyst of chloroaluminate ionic liquid and alkaline waste water.
  • ionic liquids as catalysts for alkylation reactions
  • the chloroaluminate ionic liquid alkylation process has a strong overall competitiveness, and has been adopted by the newly-built alkylated oil production device.
  • the chloroaluminate ionic liquid alkylation process still produces a small amount of spent catalyst and alkaline wastewater (ie, alkaline washing wastewater), in which about 3 kg of waste catalyst per ton of alkylated oil is produced, and 20-30 kg of alkaline washing wastewater.
  • the yield is 5% and 3% of the sulfuric acid method, respectively.
  • the waste catalyst produced by the alkylation process of chloroaluminate ionic liquid is basically the same as the composition of the new catalyst, but has a slightly reduced activity and contains acid-soluble hydrocarbons, so it has high activity, high acidity and high oil content. It is extremely necessary to carry out harmless and resourceful disposal.
  • the invention patent disclosed in CN 105457973 A discloses a method and system for treating a chloroaluminate ionic liquid spent catalyst, which first performs a digestion-neutralization reaction with a spent catalyst and an alkali solution to eliminate the activity of the spent catalyst. Acidic, and then recover the metal and oil resources in the spent catalyst.
  • the above method and system can harm the chloroaluminate ionic liquid spent catalyst to a certain extent and realize the resource utilization of the metal and the acid-soluble oil in the spent catalyst.
  • alkali washing of alkylated oil products is an important measure to ensure the quality of oil products.
  • the alkali washing wastewater discharged usually contains sodium hydroxide and sodium metaaluminate. Sodium chloride and a small amount of petroleum pollutants.
  • the alkaline washing wastewater is usually discharged to a sewage treatment system for treatment, and not only a large amount of exogenous acid is required to be neutralized, but also a large amount of aluminum hydroxide-containing materialized sludge is added after neutralization.
  • the salt load and organic load of the wastewater are high, which poses a serious impact on the stable operation of the sewage treatment system.
  • the invention provides a method and a system for treating a chloroaluminate ionic liquid spent catalyst and an alkaline wastewater, which can overcome the defects of the prior art described above, and can not only gently eliminate the activity of the spent catalyst, the process operation
  • the stability and safety are good, and the acid-soluble oil in the spent catalyst is not easily carbonized, the recovery rate of the acid-soluble oil is high, and the content of water and impurities in the acid-soluble oil recovered is low, and the quality of the oil is high.
  • the invention provides a method for treating a chloroaluminate ionic liquid spent catalyst and alkaline wastewater, comprising the following steps:
  • the present invention does not strictly limit the chloroaluminate ionic liquid spent catalyst (hereinafter referred to as waste catalyst), for example, can be derived from the alkylation reaction of C4 hydrocarbons by chloroaluminate ionic liquids, and the olefins by chloroaluminate ionic liquids.
  • waste catalyst produced by a polymerization reaction, a Friedel-Crafts alkylation reaction or a Friedel-Crafts acylation reaction.
  • the chloroaluminate ionic liquid spent catalyst is a spent catalyst produced by using a chloroaluminate ionic liquid to catalyze the production of an alkylated oil by carbon four;
  • the chloroaluminate ionic liquid spent catalyst has a viscosity of up to 600 -800 mPa ⁇ s, the active components are mainly aluminum chloride, copper chloride, etc., and other components are mainly acid-soluble hydrocarbons (ie, acid-soluble oils).
  • the inventors have found through research that the above-mentioned prior art direct addition of a base to digestion-neutralization of the spent catalyst may result in a very intense reaction process, which may be due to the fact that the main active component of the chloroaluminate ionic liquid spent catalyst is chlorinated.
  • Aluminum has a higher hydrolysis reaction rate, and is rapidly hydrolyzed to form hydrogen chloride after contact with water to make the hydrolyzate strongly acidic. At the same time, the exothermic hydrolysis reaction increases the hydrolysis reaction rate constant and further increases the hydrolysis reaction of aluminum chloride. rate.
  • a strong base is directly added during the hydrolysis of aluminum chloride, and the neutralization reaction of the strong base and hydrogen chloride releases a large amount of heat, further increasing the hydrolysis reaction rate of the aluminum chloride; if the heat is not dissipated in time, the instantaneous intense heat release Localized high temperatures are formed, resulting in the carbonization of acid-soluble oils and the formation of soot and hydrogen chloride mist, in addition to the risk of explosion.
  • the chloroaluminate ionic liquid spent catalyst is mixed with concentrated brine to carry out a hydrolysis reaction before the neutralization reaction of the spent catalyst with the alkali solution; it is found that a large amount of concentrated brine can be used in the hydrolysis process of the spent catalyst.
  • the heat generated by the hydrolysis reaction is rapidly dispersed to break the self-acceleration mechanism of the hydrolysis reaction; at the same time, the high concentration of chloride ions in the concentrated brine increases the concentration of the hydrolysis product, and has a certain inhibitory effect on the hydrolysis reaction.
  • the above method can not only gently eliminate the activity of the spent catalyst, but also eliminate the promotion effect of the heat of neutralization reaction on the hydrolysis reaction rate, making the process operation more stable and safe; and thus, the present invention has been completed.
  • the hydrolysis reaction is mainly used to completely eliminate the residual activity of the chloroaluminate ionic liquid spent catalyst; specifically, when the residual activity is completely eliminated, the acid-soluble oil is most likely to be separated, acidic
  • the pH of the hydrolyzate generally stabilizes at 2.5-2.8, which is the end of the hydrolysis reaction.
  • the content of sodium chloride in the concentrated brine may be 15-22% by weight; in addition, the volume ratio of the waste product of the chloroaluminate ionic liquid spent catalyst to the concentrated brine may be 1: ( 50-60).
  • the volume ratio of the chloroaluminate ionic liquid spent catalyst to the concentrated brine can be set to 1: (50-60) ).
  • the higher the mass content of sodium chloride in the concentrated brine the milder the hydrolysis reaction of the spent catalyst; however, when the content of sodium chloride in the concentrated brine is higher than 22% by weight, the concentration of chloride ions in the hydrolyzate is too high. Thereby, sodium chloride crystals are precipitated; when the content of sodium chloride in the concentrated brine is less than 15% by weight, the temperature rise of the hydrolysis reaction system becomes conspicuous. Therefore, the content of sodium chloride in the concentrated brine can be set to 15 to 22% by weight.
  • the inventors have found through research that the prior art adopts a full mixed-flow reactor for digestion-neutralization reaction, which leads to carbonization of acid-soluble oil and thus a low recovery rate, which may be due to the fact that the viscosity of the spent catalyst is high, The concentrated brine is in the form of droplets.
  • the mass transfer between the active component and the moisture is a controlling factor; due to the coating of the active component by the acid-soluble hydrocarbon in the spent catalyst, the activity is made.
  • the mass transfer between the component and the moisture is weakened, which facilitates the gentle progress of the hydrolysis reaction.
  • the separation of the acid-soluble hydrocarbon from the active component is accelerated, the mass transfer between the active component and the water body is enhanced, and the hydrolysis reaction rate is increased.
  • the hydrolysis reaction process is more intense; at the same time, the acid-soluble oil formed is also trapped in the reaction system, which is easy to cause carbonization, and further reduces the recovery rate of the acid-soluble oil. Therefore, it is advantageous to make the materials gently contact and react during the hydrolysis reaction stage, as much as possible to reduce the backmixing of the materials.
  • An embodiment of the present invention is to carry out the above hydrolysis reaction in a plug flow packed bed reactor to make the hydrolysis reaction milder (i.e., to achieve mild hydrolysis); at this time, the spent catalyst is contacted with the concentrated brine in a flat flow state, the material The degree of back mixing is low, the disturbance to the waste catalyst droplets is small, and the mass transfer between the active component and the moisture is weakened, which not only reduces the strength of the hydrolysis reaction, but also facilitates the separation and recovery of the acid-soluble oil.
  • the present invention fills a structured packing in a flat push-flow packed bed reactor, which utilizes the high viscosity characteristics of the spent catalyst, the boundary layer characteristics on the surface of the filler, and the retention of the catalyst by the filler; The feed amount is small, and it flows in a laminar flow on the surface of the structured packing, and forms a thick laminar boundary layer.
  • the large viscous force makes the sedimentation rate of the spent catalyst be effectively controlled.
  • the mass transfer resistance between the materials increases, so the mass transfer efficiency between the spent catalyst and the concentrated brine is also effectively controlled.
  • the material circulation hole of the structured packing is uniform, and the channeling phenomenon is not easy to occur.
  • the spent catalyst is evenly distributed in the pores of the structured packing, forming a large number of micro-element reaction environments, and the contact time of the large amount of concentrated brine with the spent catalyst is long, thereby ensuring complete hydrolysis of the spent catalyst.
  • the porosity and specific surface area of the structured packing have a great influence on the hydrolysis reaction; when the porosity is too low or the specific surface area is too large, there is a risk that the acid-soluble oil and impurities block the pores of the filler; the porosity is too high or the specific surface area is excessive In hours, the interception effect on the spent catalyst is weakened, and there is a risk that the hydrolysis reaction is incomplete.
  • the porosity of the structured packing in 0.95-0.97m 3 / m 3 i.e., a pore volume of structured packing 3 per m of 0.95-0.97m 3
  • a specific surface area 300-500m 2 / m 3 i.e., the structured packing per m 3
  • the rate of the hydrolysis reaction is well controlled, and the pore clogging is not easily caused, and the hydrolysis reaction is easily carried out completely.
  • the structured packing may be an oleophobic filler and may have a sloping plate structure; the structured packing may also promote coarse granulation of the acid-soluble oil droplets, so that the large-particle oil droplets are more easily floated, thereby facilitating the recovery of the acid-soluble oil. .
  • the structured packing may be, for example, a Y-shaped corrugated orifice structured packing, and the inclination angle of the corrugation and the axis may be about 45°, so that the intercepting effect of the spent catalyst droplets is good.
  • the structured packing material may be polyethylene (PE), polyvinyl chloride (PVC) or polyvinylidene fluoride (PVDF), which is oleophobic and resistant to acid and chlorine, which is favorable for coarse granulation of acid-soluble oil, thereby It is convenient for acid-soluble oil recovery.
  • the space velocity may be 0.25 - 0.5 h -1 .
  • the pH value can be stabilized at 2.5-2.8; when the space velocity is 0.25h -1 , the acid hydrolysis liquid has the lowest oil content, and the recovered acid-soluble oil can be recovered. Achieve the most.
  • the active components such as aluminum chloride in the spent catalyst are completely deactivated, and finally enter the acidic hydrolyzate; the acid-soluble oil in the spent catalyst can be settled by a conventional method such as sedimentation. Recycle and reuse.
  • the acidic hydrolyzate formed by the hydrolysis reaction has high sodium chloride content, strong acidity and contains metal resources, which can be subsequently neutralized to achieve harmlessness and resource utilization.
  • the alkaline hydrolyzate can be used to neutralize the acidic hydrolyzate formed by the hydrolysis reaction; the present invention does not strictly limit the alkaline wastewater, for example, it can be used to catalyze the carbon four by using a chloroaluminate ionic liquid.
  • the alkali washing wastewater produced by the production of alkylated oil has a sodium hydroxide content of about 10-15% by weight.
  • the acidic alkaline hydrolyzate is mainly composed of metal hydroxide flocs and concentrated brine in the weak alkaline neutralization solution after neutralization, and is controlled to be weakly alkaline to facilitate formation of metal hydroxide flocs as much as possible, such as pH. Above 7.5, it can be observed that the formation of flocs is substantially stable as a criterion for completion of the neutralization reaction. In the specific operation, the pH of the neutralized solution is stabilized at 8.0-8.5, which is the end point of the neutralization reaction.
  • the concentration of the lye is not strictly limited, and the concentration of the lye can be appropriately adjusted according to the concentration of sodium chloride in the neutralizing solution; when the alkaline wastewater is insufficient to meet the requirements of the neutralization reaction, The exogenous lye is supplemented, and the alkaline wastewater and the exogenous alkali together constitute an alkali solution for neutralizing the acidic hydrolyzate.
  • the concentration of sodium chloride in the neutralization solution when the concentration of sodium chloride in the neutralization solution is less than 15% by weight, the concentration of the alkali solution can be increased; when the concentration of sodium chloride in the neutralization solution is higher than 22% by weight, the concentration of the alkali solution can be lowered.
  • the concentration of the exogenous alkali solution is not strictly limited, and the content of sodium hydroxide in the exogenous alkali solution may be 25-35 wt%.
  • metal ions such as aluminum and copper in the acidic hydrolyzate are combined with hydroxide ions in the lye to form metal hydroxide flocs; at the same time, sodium ions in the alkali solution and the acidic hydrolyzate A high concentration of sodium chloride (ie, concentrated brine) formed by chloride ions, and a small amount of oil carried in the acidic hydrolyzate is also transferred to the neutralizing solution.
  • sodium chloride ie, concentrated brine
  • the neutralization reaction can be carried out in a full mixed flow reactor; the full mixed flow reactor can perform a rapid neutralization reaction, thereby being able to reduce the volume of the reactor.
  • the space velocity of the full mixed flow reactor can be 1-2 h -1 ; wherein when the space velocity of the full mixed flow reactor reaches 2 h -1 , the acidic hydrolyzate is completely neutralized, and the pH of the neutralized liquid is stabilized at 8.0-8.5, which is the end point of the neutralization reaction; when the space velocity is increased to 1 h -1 , the yield of the metal hydroxide flocs in the neutralization liquid is the highest, and the content of the metal hydroxide flocs reaches 2.5 to 3 wt%.
  • the main composition of the neutralized liquid formed by the above neutralization reaction is metal hydroxide flocs and concentrated brine, and subsequent flocculation is used for sedimentation separation, and the metal hydroxide flocs and concentrated brine can be initially separated.
  • the concentrated brine can be recovered for the hydrolysis reaction of the spent catalyst; the metal hydroxide floc is concentrated and concentrated to reduce the volume, which reduces the load of the subsequent dehydration treatment.
  • the flocculating agent is added to the neutralizing liquid, and the loose small particle metal hydroxide flocs can be converted into dense large-particle flocs by adsorption bridging (promoting mutual interaction between the particles) Bonded) is more conducive to the precipitation of metal hydroxide flocs.
  • the mixing mode of the neutralizing liquid and the flocculating agent is not strictly limited.
  • the pipe mixer can be used for thorough mixing, and then the flocculation and sedimentation device is used for sedimentation separation of the floc and the concentrated brine.
  • the flocculating agent used in the present invention is not strictly limited.
  • an anionic polyacrylamide flocculating agent can be used, which is more suitable for flocculation of metal hydroxide flocs.
  • the relative molecular weight of the anionic polyacrylamide flocculant may range from 600 to 18 million, further from 12 to 18 million; and the charge density may range from 10 to 40%, further from 10 to 30%.
  • the use of the above anionic polyacrylamide flocculant is more advantageous for promoting mutual bonding between aluminum hydroxide and copper hydroxide particles, thereby facilitating the formation of larger flocs.
  • the amount of flocculant used is based on the ability to effectively promote the formation and settlement of flocs. Further, the study found that when 20 g or more of the above flocculating agent is added per ton of neutralizing liquid, the flocs formed are coarse and dense, and the sedimentation performance is good; when the amount of flocculating agent added per ton of neutralizing liquid exceeds 30 g, The flocculation settling performance is not improved and is not economical. Therefore, the dosage of the above flocculating agent can be set to be 20-30 g per flone of the neutralizing liquid.
  • the concentrated floc formed may have a concentrated brine content of about 85-90 wt%, and the metal hydroxide has a solid content of about 10-15 wt%.
  • a small amount of oil in the neutralizing liquid will be concentrated in the concentrated brine phase, so the concentrated floc has a low oil content and is cleaner, which facilitates its subsequent recycling.
  • the present invention dehydrates the concentrated flocs to reduce the total amount of the metal hydroxide system while returning the concentrated brine.
  • the dehydration treatment method of the concentrated flocs is not strictly limited, and a conventional mechanical dehydration method such as plate-frame pressure filtration or centrifugal dehydration may be employed.
  • the metal hydroxide concentrated floc has large particles, and the water contained therein is mainly free water, and the separation of the metal hydroxide solid and the concentrated brine can be achieved by pressure filtration or centrifugal filtration.
  • the operating pressure can be about 0.45 MPa; when dewatering by centrifugation, the separation factor of centrifugal dewatering can be about 3,000.
  • the moisture content of the wet slag (ie, metal hydroxide concentrated floc) formed by the above dehydration treatment is about 60-70 wt%; the concentrated brine formed by the dehydration treatment can be reused for the above hydrolysis reaction.
  • the wet solid residue formed by the dehydration treatment is mainly capillary water
  • the thin layer drying technology couples the principle of conduction and radiation drying, generally adopts the indirect heating method of hot fluid, which has a faster vaporization rate of moisture in the wet solid residue;
  • the low temperature dehumidification drying technology is based on the principle of convection drying, generally adopting electric direct heating method, gas
  • the dehumidification speed is slower than the thin layer drying, the equipment investment is low and the process operation is simple.
  • a thin layer drying technique is preferred.
  • the latent heat of water vapor can be recovered to reduce energy consumption; the condensed water generated in the heat recovery stage is less polluted and can be reused for lye and flocculant solution.
  • the dried slag formed by the above drying treatment has a water content of 10 to 20% by weight.
  • the method for treating chloroaluminate ionic liquid spent catalyst and alkaline waste water mainly adopts the main technical route of “mild hydrolysis-rapid neutralization-flocculation sedimentation-mechanical dehydration-dehumidification drying”, which is simple in operation and capable of Mildly eliminate the activity of spent catalyst, while avoiding the impact of alkaline wastewater on the sewage treatment system, the stability and safety of the overall process operation, the metal and oil resources in the spent catalyst are effectively recovered and utilized, and the intermediate product It is also recycled, and the process cost is relatively low, which is conducive to promoting the green upgrade of the ionic liquid alkylation process.
  • the present invention also provides a system for carrying out the above method, comprising a hydrolysis reactor, a neutralization reactor, a flocculation sedimentation system, a mechanical dewatering device, and a drying device;
  • the hydrolysis reactor is used for mixing a chloroaluminate ionic liquid spent catalyst with concentrated brine to carry out a hydrolysis reaction;
  • the neutralization reactor is connected to the hydrolysis reactor for mixing the acidic hydrolyzate formed by the hydrolysis reaction with an alkali solution containing alkaline wastewater for neutralization reaction;
  • the flocculation sedimentation system is connected to the neutralization reactor for thoroughly mixing the neutralized liquid generated by the neutralization reaction with a flocculating agent and performing sedimentation separation;
  • the mechanical dewatering device is connected to the flocculation and sedimentation system for dehydrating the concentrated flocs formed by the sedimentation separation;
  • the drying device is connected to the mechanical dewatering device for drying the wet solid residue formed by the dehydration treatment.
  • the hydrolysis reactor is a plug flow packed bed reactor, the plug flow packed bed reactor packed with a structured packing, the packing is structured porosity 0.95-0.97m 3 / m 3, The specific surface area is 300-500 m 2 /m 3 .
  • the present invention does not strictly limit the specific structure of the hydrolysis reactor, and a hydrolysis reaction apparatus known in the art and commonly used can be employed.
  • the hydrolysis reactor used includes a casing, and an annular oil collecting groove, a water distributor for distributing concentrated brine, and a distribution of aluminum chloride for the upper portion from the top to the bottom of the casing.
  • a distributor for an acid ionic liquid spent catalyst a filler carrier for supporting a filler is disposed at a lower portion of the casing, and an exhaust port is disposed at a top of the casing, and a sidewall of the casing is disposed at a sidewall of the casing
  • the bottom of the housing is provided with a liquid outlet.
  • the spent catalyst In view of the extremely strong acidity of the spent catalyst and the viscosity of up to 600-800 mPa ⁇ s, and containing a small amount of mechanical impurities, in order to prevent clogging and corrosion, it is preferably transported by a mechanical diaphragm pump made of fluoroplastic; in addition, in concentrated brine
  • the sodium chloride content is as high as 15-22% by weight, and the corrosion is strong, and it is preferably conveyed by a centrifugal pump made of stainless steel.
  • the spent catalyst is mixed with concentrated brine to carry out a hydrolysis reaction, and the acid-soluble hydrocarbon in the spent catalyst is separated from the active component, and the formed acid-soluble oil is floated to the liquid surface, collected through the annular oil collection tank, and then discharged.
  • the oil port and its pipeline flow into the oil storage tank for refining.
  • the water inlet and the water distributor are respectively disposed above the feed port and the distributor, which is advantageous not only for the dispersion of the spent catalyst by the concentrated brine but also for the hydrolysis reaction of the spent catalyst. Keep away from the acid-soluble oil layer and avoid the influence of partial heat release of hydrolysis on the quality and recovery of acid-soluble oil.
  • the active components contained in the spent catalyst and the acid-soluble hydrocarbons produce volatile organic pollutants (VOCs) and hydrogen chloride during the hydrolysis process, which are concentrated at the top of the hydrolysis reactor, in order to avoid contamination of the air,
  • VOCs volatile organic pollutants
  • the top of the hydrolysis reactor is provided with an exhaust port, and the gas is led to the water seal of the concentrated brine storage tank.
  • the concentrated brine in the concentrated brine storage tank can absorb these gaseous pollutants, and can also use the liquid level for water sealing;
  • the seal also provides a positive pressure to the hydrolysis reactor, which promotes the reabsorption of these contaminants by the acidic hydrolysate.
  • the structure of the water distributor of the hydrolysis reactor is not strictly limited as long as it can uniformly distribute the concentrated brine to the hydrolysis reactor.
  • the water distributor comprises a water distribution pipe, and a plurality of water distribution pipes arranged in parallel and equally spaced are respectively disposed on two sides of the water distribution pipe, at the bottom of each water distribution pipe A plurality of water distribution holes are distributed, and the total opening area of the water distribution holes accounts for more than 1% of the cross-sectional area of the hydrolysis reactor.
  • the water distributor is a fishbone type; wherein the spacing between adjacent water distribution pipes can be set to be more than 5 cm, thereby avoiding affecting the floating and collecting of the acid-soluble oil; moreover, the water distribution hole on the water distribution pipe
  • the setting method is not strictly limited, and a plurality of cloth water holes can be set at equal intervals, and the apertures of the plurality of cloth holes can be set to be the same.
  • the water distributor having the above structure has a large opening area and a large number of openings, thereby facilitating the uniform distribution of the concentrated brine; in addition, a laminar flow is formed in the hydrolysis reactor due to the small flow velocity of the outlet hole of the cloth and low back mixing. The flow, the mass transfer between the spent catalyst and the spent catalyst is weakened, and the acid-soluble oil layer on the hydrolyzed liquid surface is less disturbed, which is more favorable for the recovery of the acid-soluble oil.
  • the structure of the distributor of the hydrolysis reactor is not strictly limited as long as it can uniformly distribute the spent catalyst to the hydrolysis reactor.
  • the hopper includes a fabric main pipe, and a plurality of concentric and equally spaced semicircular cloth branch pipes are respectively disposed on two sides of the cloth main pipe at the bottom of each semicircular cloth branch pipe.
  • a plurality of cloth holes are distributed, and the total opening area of the cloth holes accounts for more than 2% of the cross-sectional area of the hydrolysis reactor.
  • the distributor is a ring type; wherein the spacing between adjacent cloth branches can be set to 5 cm or more, thereby avoiding affecting the floating and collecting of the acid-soluble oil; in addition, the arrangement of the cloth holes on the cloth branch pipe is not strict.
  • the plurality of cloth holes may be disposed at equal intervals, and the apertures of the plurality of cloth holes may be set to be the same, and the inner diameter of the cloth holes may be set to, for example, 3-5 mm.
  • the distributor having the above structure has a large opening area and a large number of cloth holes, thereby facilitating uniformity of the waste catalyst cloth; in addition, since the inner diameter of the cloth opening is small, the spent catalyst is extruded as small droplets, which is more advantageous in the concentrated brine. Dispersed.
  • the neutralization reactor is used to mix the acidic hydrolyzate produced by the hydrolysis reaction with an alkali solution containing alkaline wastewater for neutralization reaction; the specific structure of the neutralization reactor is not strictly limited, and the field may be employed. Conventional neutralization reactor.
  • the neutralization reactor is a full mixed flow reactor;
  • the neutralization reactor includes a casing, and a cloth for distributing lye is sequentially disposed from top to bottom in an upper portion of the casing.
  • a water device and a distributor for distributing the neutralizing liquid, a side-feeding agitator is provided in a middle portion of the casing, and an exhaust port is provided at a top of the casing, and a side wall of the casing is provided
  • the inventors' research has shown that the alkali inlet port and the water distributor of the neutralization reactor are respectively disposed above the liquid inlet port and the distributor, so that the position of the metal hydroxide floc formed by the neutralization reaction is low. Therefore, it is not easy to block the water distributor.
  • the use of a side-feeding agitator accelerates the mass transfer and neutralization reaction between the acidic hydrolyzate and the lye, and also prevents premature precipitation of the flocs to block the outlet and its piping.
  • the high-chlorine-containing acidic hydrolyzate can be transported by a centrifugal pump made of fluoroplastic material; the alkali-washing wastewater and the exogenous alkali liquid are high in chlorine and high in alkali, and need to be accurately matched with the acidic hydrolyzate to achieve Therefore, it is preferred to use a metering pump of a fluoroplastic material to transport the alkaline washing wastewater and the external alkali liquor.
  • the neutralization process causes enrichment of VOCs at the top of the neutralization reactor; to prevent air pollution, an exhaust port may be provided at the top of the neutralization reactor.
  • the gas is led to the water seal of the concentrated brine storage tank.
  • the concentrated brine in the concentrated brine storage tank can absorb these gaseous pollutants or use the liquid level for water sealing; the water seal can also provide positive pressure for the neutralization reactor. , thereby promoting the reabsorption of these contaminants by the neutralizing solution.
  • the structure of the water distributor and the distributor of the neutralization reactor is not strictly limited, and as long as the alkali liquid and the acidic hydrolyzate can be uniformly distributed in the neutralization reactor, the same structure as in the hydrolysis reactor can be employed;
  • the water discharge hole in the water distributor has a total opening area of more than 1% of the cross-sectional area of the neutralization reactor, the total opening area of the cloth hole in the distributor accounts for more than 2% of the cross-sectional area of the neutralization reactor.
  • the water discharge device Since the water discharge device has a large opening area and a large number of openings, the alkaline washing wastewater and the external alkali are promoted.
  • the liquid is evenly distributed in the neutralization reactor; in addition, the acidic hydrolyzate is dispensed in the neutralization reactor via the above-mentioned ring type distributor, and the distributor has a small opening area, a small number of cloth ports, and a small inner diameter. Partial turbulence is formed after the liquid is discharged, which contributes to mass transfer and neutralization reaction between the acidic hydrolyzate and the lye.
  • the flocculation sedimentation system is used to thoroughly mix the neutralization liquid produced by the neutralization reaction with the flocculant and perform sedimentation separation;
  • the specific structure of the flocculation sedimentation system is not strictly limited, and a structure conventional in the art may be employed.
  • the flocculation sedimentation system comprises a pipeline mixer and a flocculation sedimentation device arranged in sequence, the flocculation sedimentation device comprising a sealed casing, and an annular overflow weir and a center are arranged inside the sealed casing a tube and a cloth tube, the cloth tube is disposed inside the center tube, an umbrella type baffle is disposed at a bottom of the center tube, and an exhaust port is provided at a top of the sealing shell, in the seal
  • the side wall of the casing is provided with a water outlet and a feed port, the water outlet is in communication with the annular overflow weir, the feed port is in communication with the cloth pipe, and is provided at the bottom of the sealed casing Slag mouth.
  • the outlet of the neutralization reactor is connected to the inlet of the pipeline mixer through the pipeline, and a dosing port is provided on the connecting pipe of the neutralization reactor outlet and the pipeline mixer inlet, and the flocculating agent is prepared.
  • the dispensing port is connected to the dosing port via a stainless steel metering pump and tubing.
  • the pipe mixer facilitates sufficient contact between the neutralizing liquid and the flocculating agent; in addition, the dosing pump of stainless steel is used for the dosing, so that the flocculating agent and the neutralizing liquid are accurately matched to achieve an optimum ratio. Flocculation effect.
  • the flocculation and sedimentation device having the above structure is in the form of a sealed vertical flow type sedimentation tank; the neutralization liquid containing the flocs is thoroughly mixed with the flocculant through the pipeline mixer, and is subjected to self-flow into the flocculation and sedimentation device for precipitation separation.
  • the water content of the concentrated flocs is reduced, the processing load of the subsequent mechanical dewatering device is reduced, and the precipitated concentrated brine can be reused for the hydrolysis reactor.
  • a sealed form is adopted, and an exhaust port is provided at the top to guide the gas to the brine storage tank for water sealing.
  • the flocculation and sedimentation device in the form of the vertical flow sedimentation tank is used to separate the concentrated brine from the flocs; the neutralization liquid is mixed with the flocculant and then enters through the feed port.
  • the flocculation and sedimentation device, the cloth pipe drives the neutralization liquid downward into the central pipe, and the metal-type hydroxide flocs are sedimented and concentrated to the bottom of the flocculation and sedimentation device through the umbrella baffle; meanwhile, the concentrated brine flows to the top of the flocculation and sedimentation device.
  • the use of a mechanical dewatering device to dewater the concentrated flocs can significantly reduce the amount of slag. Since the concentrated floc has a solid content of about 2-3 wt% and contains concentrated brine, it can be transported using a stainless steel screw pump. In addition, the water in the concentrated flocs is mainly free water, so a good dewatering effect can be obtained by using a conventional plate and frame filter press or a centrifugal dewatering machine. Since the plate and frame filter press has the disadvantages of large land occupation, long processing time, and inability to continuously operate, the mechanical dewatering device is preferably a centrifugal dewatering machine, and the separation factor can be about 3000, at which time the concentrated floc can be prepared into water. The rate is 60-70% wet solid residue.
  • the system of the present invention is provided with a drying device for drying the wet slag formed by the mechanical dewatering device.
  • the wet slag can be transported by using a screw conveyor; the conveying method is relatively clean, and the phenomenon of slag dropping in the belt transmission is avoided.
  • the drying device may be a thin layer drying machine or a low temperature dehumidifying drying machine capable of drying the wet solid residue into a dry solid residue having a water content of 10-20%. Since the moisture in the dry slag is mainly crystallization water, it is not only inefficient and uneconomical to continue to lower the water content.
  • the system of the present invention may further comprise a heat recovery device (ie, a condensate storage tank) for recovering the condensed water produced by the above-described drying device; since the recovered condensed water has a low pollution load, it can be reused Preparation of source lye and flocculant.
  • a heat recovery device ie, a condensate storage tank
  • system of the present invention may include other supporting components in addition to the above-mentioned main body components, such as spent catalyst storage tanks, concentrated brine storage tanks, alkaline washing wastewater storage tanks, exogenous alkali liquid preparation tanks, flocculating agents.
  • Formulation tanks, condensate storage tanks, sewage oil storage tanks, and various pumps and conveyors for conveying materials, etc. can all be carried out using conventional apparatus or components in the art, and can be set in a conventional manner.
  • the spent catalyst storage tank comprises a tank body, and a side-feeding agitator is arranged inside the tank body, and a feeding port and a discharging port are arranged at a lower end of the tank side wall, and an air discharging port is arranged at the bottom of the tank body.
  • a gas inlet is arranged at the top of the tank; wherein the side-feeding agitator is used for homogenizing the average amount of spent catalyst from different time periods, and the gas inlet is used for protecting the top of the spent catalyst storage tank from nitrogen gas to avoid The spent catalyst is in contact with moisture in the air to prevent the hydrolysis from exploding.
  • the concentrated brine storage tank comprises a tank body and a water sealing tube, and a water inlet is arranged at an upper end of the side wall of the tank body, a water outlet is arranged at a lower end of the side wall of the tank body, and an air outlet is provided at the bottom of the tank body,
  • the top of the tank is provided with a water seal, and the water seal tube is connected with the water seal.
  • the setting of the concentrated brine storage tank not only provides space for the storage of the concentrated brine of the intermediate product, but also provides the raw material for the hydrolysis reaction, which is the key node for the recycling of the intermediate products of the whole system; at the same time, the hydrolysis reactor can be controlled by the water seal, and the neutralization can be controlled.
  • the escape of gaseous pollutants in the reactor and the flocculation and sedimentation device avoids air pollution.
  • the alkaline washing wastewater storage tank comprises a tank body, and a side-intake agitator is arranged inside the tank body, and a water inlet and a water outlet are arranged at a lower end of the tank side wall, and an air outlet is arranged at the bottom of the tank body;
  • the side-feeding agitator is used to homogenize the alkaline washing wastewater from different time periods.
  • the condensed water storage tank includes a tank body, and a water inlet is provided at an upper end of the side wall of the tank body, a condensed water outlet is provided at a lower end of the side wall of the tank body, and an venting opening is provided at a bottom of the tank body.
  • the condensate storage tank provides space for the storage of intermediate condensate, and provides a water source for the preparation of the external lye and flocculant, and is an important node for the recycling of the intermediate products of the whole system.
  • the system of the present invention includes a mechanical diaphragm pump and a centrifugal pump, the spent catalyst storage tank being connected to a feed port of the hydrolysis reactor through the mechanical diaphragm pump, the concentrated brine storage tank passing through the centrifugal pump It is connected to the water inlet of the hydrolysis reactor, and the oil discharge port of the hydrolysis reactor is connected to the sewage oil storage tank.
  • the system of the present invention includes a centrifugal pump and a metering pump, and a liquid outlet of the hydrolysis reactor is connected to an inlet of the neutralization reactor through the centrifugal pump, the alkaline washing wastewater storage tank and the outside
  • the source lye preparation tank is respectively connected to the inlet port of the neutralization reactor through the metering pump, and the outlet port of the neutralization reactor is connected to the pipeline mixer.
  • the system of the present invention includes a metering pump that is connected to the water inlet of the external lye preparation tank and the water inlet of the flocculant preparation tank by the metering pump, respectively.
  • the metering pump is used to transport the condensed water, which is convenient for precise control of the concentration of the external lye and flocculant.
  • the exhaust port of the hydrolysis reactor, the exhaust port of the neutralization reactor, the water outlet and the exhaust port of the flocculation sedimentation system are respectively connected to the water seal of the brine storage tank through a pipeline.
  • the flocculation sedimentation system and the mechanical dewatering device have a concentrated brine outlet, and the concentrated brine outlet is connected to the concentrated brine storage tank to facilitate reuse of the concentrated brine.
  • the system of the present invention is directed to the characteristics of a chloroaluminate ionic liquid spent catalyst and an alkaline washing wastewater, which utilizes a hydrolysis reactor and a neutralization reactor to achieve detoxification of waste catalysts and caustic washing wastewater and oils.
  • the operation of the whole system is mild, the operation process is safe, there is no new pollution source, and the recovery rate of resources is high, especially the recovered acid-soluble oil has low content of water and impurities, and the quality of the oil is high.
  • FIG. 1 is a process flow diagram of treating a chloroaluminate ionic liquid spent catalyst and alkaline wastewater according to an embodiment of the present invention
  • FIG. 2 is a schematic structural view of a system for treating a chloroaluminate ionic liquid spent catalyst and an alkaline wastewater according to an embodiment of the present invention
  • FIG. 3 is a schematic structural view of a hydrolysis reactor according to an embodiment of the present invention.
  • Figure 4 is a cross-sectional view taken along line A-A of Figure 3;
  • FIG. 5 is a schematic structural view of an annular oil collecting groove of a hydrolysis reactor according to an embodiment of the present invention.
  • FIG. 6 is a schematic structural view of a water distributor according to an embodiment of the present invention.
  • FIG. 7 is a schematic structural view of a distributor according to an embodiment of the present invention.
  • Figure 8 is a cross-sectional view taken along line B-B of Figure 7;
  • Figure 9 is a schematic structural view of a neutralization reactor according to an embodiment of the present invention.
  • Figure 10 is a schematic view showing the structure of a flocculation and sedimentation apparatus according to an embodiment of the present invention.
  • 3 flocculation and sedimentation device; 31: sealed casing; 32: annular overflow weir; 33: central pipe; 34: cloth pipe; 35: umbrella baffle; 36: exhaust port; 37: water outlet; 38: Feed port; 39: slag outlet;
  • 61 spent catalyst storage tank; 611: gas inlet; 62: concentrated brine storage tank; 63: alkaline washing wastewater storage tank; 64: exogenous alkali liquid preparation tank; 65: flocculant preparation tank; 66: condensed water storage tank; 67: dirty oil storage tank;
  • 71 mechanical diaphragm pump
  • 72, 77 centrifugal pump
  • 73, 74, 75, 76 metering pump
  • 78 screw pump
  • 101 cloth water main pipe
  • 102 cloth water branch pipe
  • 201 cloth main pipe
  • 202 cloth branch pipe
  • 203 cloth hole.
  • Chloroaluminate ionic liquid spent catalyst a waste catalyst produced by using a chloroaluminate ionic liquid to catalyze the production of alkylated oil by carbon four, the viscosity is about 740 mPa ⁇ s, and the active components are mainly aluminum chloride and copper chloride.
  • the total content is about 85 wt%; the other components are acid-soluble hydrocarbons, and the content is about 15% by weight.
  • Alkaline wastewater Alkaline washing wastewater produced by the production of alkylated oil by carbon tetrachloride catalyzed by a chloroaluminate ionic liquid, the sodium hydroxide concentration is about 12% by weight.
  • the method for treating the above chloroaluminate ionic liquid spent catalyst and alkaline wastewater comprises: firstly, mixing a chloroaluminate ionic liquid spent catalyst with a concentrated brine to carry out a hydrolysis reaction until the residual activity of the spent catalyst is completely eliminated; An acidic hydrolyzate and an acid-soluble oil are formed, and the acid-soluble oil is separated from the acidic hydrolyzate to be separated into an upper layer and recovered; then, the acidic hydrolyzate, the alkali-washing wastewater, and the prepared exogenous alkali solution are mixed for neutralization reaction until the system is It is weakly alkaline, and generates a neutralization liquid containing metal hydroxide flocs; the neutralization liquid is thoroughly mixed with the flocculant, and then sedimentation is separated, and concentrated flocs are formed at the bottom, and the concentrated brine is separated and used for waste catalyst.
  • the hydrolysis reaction the above-mentioned concentrated floc is mechanically dehydrated to form a wet solid residue having a water content of about 60-70% by weight, and the concentrated brine separated from the concentrated floc is reused for the hydrolysis reaction of the spent catalyst;
  • the slag is dried to form a dried slag having a water content of about 10-20% by weight, and the water vapor generated during the drying process is condensed and returned to the external lye and the flocculant solution.
  • the amount of spent catalyst discharged in the production process is 2140 tons/year, and the spent catalyst is collected in the spent catalyst storage tank for storage. At the same time, the amount of caustic washing wastewater discharged from the plant during the production process was 6,340 tons/year.
  • the method for treating a chloroaluminate ionic liquid spent catalyst and alkaline wastewater in the present embodiment is as follows:
  • a sodium chloride solution (ie, concentrated brine) having a concentration of about 15% by weight is prepared in a concentrated brine storage tank and stored for use.
  • a sodium hydroxide solution (ie, an exogenous alkali solution) having a concentration of about 30% by weight is prepared in the lye preparation tank, and stored for use.
  • a flocculant solution having a concentration of about 0.5% by weight is prepared in a flocculating agent preparation tank and stored for use; wherein the flocculating agent is an anionic polyacrylamide having a relative molecular weight of 15 million and a charge density of 20%.
  • the above reagents are prepared by using fresh water (for example, tap water) before the start of the operation; after the operation, the lye and the flocculant are prepared by using condensed water from a drying device, and the concentrated brine is prepared by using a flocculation sedimentation device and a mechanical dewatering device. Concentrated brine.
  • the 255kg/h spent catalyst was lifted by a fluoroplastic mechanical diaphragm pump, and the 12457kg/h concentrated brine was lifted by a stainless steel centrifugal pump.
  • the spent catalyst and concentrated brine were fed into the hydrolysis reactor for hydrolysis reaction at a ratio of 1:50. .
  • the hydrolysis reaction is carried out in a plug-in packed bed reactor, and the packed bed reactor is filled with a structured packing, and the spent catalyst and the concentrated brine are hydrolyzed in the packing layer in a flow state of a flat push flow; wherein the structured packing PVC material selected Y-corrugated structured packing orifice, a specific surface area of 350m 2 / m 3, a porosity of 0.95m 3 / m 3, space velocity hydrolysis reactor packing layer is controlled 0.25h -1.
  • the pH of the product to be hydrolyzed is stabilized at about 2.6, and the residual activity of the spent catalyst is completely eliminated.
  • the hydrolysis reaction product is subjected to sedimentation separation to obtain an acidic hydrolyzate and an acid-soluble oil respectively; wherein the pH of the acidic hydrolyzate is about 2.6, and the oil content is about 120 mg/L; at the same time, the acid-soluble oil of about 40 kg/h passes through the self-flow. Recycled into a slop tank for storage.
  • the acid-soluble oil is composed of a cyclopentadiene compound which can be periodically sent to a delayed coker for reuse as a raw material.
  • the acidic hydrolyzate of 12672kg/h is lifted by the fluoroplastic centrifugal pump.
  • the 754kg/h alkaline washing wastewater and the 251kg/h exogenous alkali liquid are lifted by the fluoroplastic metering pump.
  • the acidic hydrolyzate, the alkaline washing wastewater and the external lye are 50: A 3:1 feed volume ratio enters the neutralization reactor for neutralization.
  • the neutralization reaction is carried out in a full mixed-flow reactor, and the acidic hydrolyzate, the alkali-washing wastewater and the exogenous alkali solution are subjected to a rapid neutralization reaction in a fully mixed flow state; wherein the space velocity of the neutralization reactor is controlled at 1 h -1
  • the space velocity of the neutralization reactor is controlled at 1 h -1
  • the acidic hydrolyzate is completely neutralized.
  • the oil content of the neutralizing liquid is about 120 mg/L
  • the sodium chloride content is about 20 wt%
  • the aluminum hydroxide/hydrated copper floc The content of the body is about 2.8 wt%.
  • the volume of the concentrated floc layer accounts for about 25% of the volume of the material in the flocculation and sedimentation device, and the concentrated brine content of the concentrated floc is about 90% by weight.
  • 75 wt% of the volume of the flocculation and sedimentation device is concentrated brine, and the petroleum content is about 150 mg/L.
  • the concentrated brine flows into the concentrated brine storage tank and is reused for the hydrolysis reactor.
  • the concentrated flocs are transported into a centrifugal dewatering machine (ie mechanical dewatering device) through a stainless steel screw pump for dehydration treatment, wherein the separation factor of the centrifugal dewatering machine is about 3000; the moisture content of the dewatering is about 70 wt%, and the wet solid residue is self-unloading into the material.
  • the silo the concentrated brine separated from the concentrated floc, has an oil content of 100 mg/L, and the concentrated brine flows into the concentrated brine storage tank and is reused for the hydrolysis reactor.
  • the wet solid residue in the silo was sent to a thin layer drying machine (i.e., a drying device) through a stainless steel screw conveyor to produce 454 kg/h of dry solids having a water content of 15 wt%.
  • the content of sodium chloride in the dry solid residue is about 54.7 wt%
  • the content of aluminum hydroxide is about 22.5 wt%
  • the content of copper hydroxide is about 6.7 wt%
  • the oil content is less than 1 wt%, which can be used as a general solid waste factory. Or used as a metallurgical raw material.
  • the CODcr produced by the drying process of the thin layer dryer is about 500mg/L, almost free of oil and salt, and flows into the condensate storage tank and is used for the preparation of the lye and flocculant solution.
  • FIG. 2 For the implementation of the above processing, the processing system diagram shown in FIG. 2 can also be referred to at the same time.
  • the recovery rate of the acid-soluble oil in the spent catalyst is about 90%; in addition, the water content of the acid-soluble oil recovered is about 1% by weight, and no carbon particle impurities are detected, and the oil is recovered. High quality.
  • a sodium chloride solution ie, concentrated brine having a concentration of about 22% by weight is prepared in a concentrated brine storage tank and stored for use.
  • a sodium hydroxide solution (ie, an exogenous alkali solution) having a concentration of about 30% by weight is prepared in the lye preparation tank, and stored for use.
  • a flocculant solution having a concentration of about 0.5% by weight is prepared in a flocculating agent preparation tank and stored for use; wherein the flocculating agent is an anionic polyacrylamide having a relative molecular weight of 18 million and a charge density of 10%.
  • the above reagents are prepared by using fresh water (for example, tap water) before the start of the operation; after the operation, the lye and the flocculant are prepared by using condensed water from a drying device, and the concentrated brine is prepared by using a flocculation sedimentation device and a mechanical dewatering device. Concentrated brine.
  • fresh water for example, tap water
  • the lye and the flocculant are prepared by using condensed water from a drying device
  • the concentrated brine is prepared by using a flocculation sedimentation device and a mechanical dewatering device. Concentrated brine.
  • the processing procedure and the system used can still refer to Figures 1 and 2.
  • the spent catalyst is lifted by a fluoroplastic mechanical diaphragm pump, and the concentrated brine is lifted by a stainless steel centrifugal pump.
  • the spent catalyst and the concentrated brine are fed to the hydrolysis reactor for hydrolysis reaction at a ratio of feed ratio of 1:60.
  • the hydrolysis reaction is carried out in a plug-in packed bed reactor, and the packed bed reactor is filled with a structured packing, and the spent catalyst and the concentrated brine are hydrolyzed in the packing layer in a flow state of a flat push flow; wherein the structured packing PVC material selected Y-corrugated structured packing orifice, a specific surface area of 500m 2 / m 3, a porosity of 0.97m 3 / m 3, space velocity hydrolysis reactor packing layer is controlled 0.5h -1.
  • the pH of the product to be hydrolyzed is stabilized at about 2.6, and the residual activity of the spent catalyst is completely eliminated.
  • the hydrolysis reaction product is sedimented and separated to obtain an acidic hydrolyzate and an acid-soluble oil respectively; wherein the pH of the acidic hydrolyzate is about 2.6, and the oil content is about 120 mg/L; at the same time, the acid-soluble oil is recovered by gravity flow into the sewage reservoir.
  • the acid-soluble oil is composed of a cyclopentadiene compound which can be periodically sent to a delayed coker for reuse as a raw material.
  • the acidic hydrolyzate is lifted by a fluoroplastic centrifugal pump, the alkali washing wastewater and the external alkali liquor are lifted by the fluoroplastic metering pump, and the acidic hydrolyzate, the alkali washing wastewater and the external lye are respectively entered into the neutralization reactor according to a certain feed volume ratio.
  • the neutralization reaction is carried out so that the concentration of sodium chloride in the neutralizing solution is about 30% by weight.
  • the neutralization reaction is carried out in a full mixed-flow reactor, and the acidic hydrolyzate, the alkali-washing wastewater and the exogenous alkali solution are subjected to a rapid neutralization reaction in a fully mixed flow state; wherein the space velocity of the neutralization reactor is controlled at 2 h -1
  • the space velocity of the neutralization reactor is controlled at 2 h -1
  • the pH of the neutralizing solution reaches about 8.5
  • the acidic hydrolyzate is completely neutralized.
  • the oil content of the neutralizing liquid is about 60 mg/L
  • the sodium chloride content is about 23 wt%.
  • the aluminum hydroxide/hydrated copper floc The content of the body is about 2.8 wt%.
  • the volume of the concentrated floc layer accounts for about 20% of the volume of the material in the flocculation and sedimentation device, and the concentrated brine content of the concentrated floc is about 85 wt%.
  • 97 wt% of the volume of the flocculation and sedimentation device is concentrated brine, and the petroleum content is about 50 mg/L.
  • the concentrated brine flows into the concentrated brine storage tank and is reused for the hydrolysis reactor.
  • the concentrated flocs are transported into a centrifugal dewatering machine (ie mechanical dewatering device) through a stainless steel screw pump for dehydration treatment, wherein the separation factor of the centrifugal dewatering machine is about 3000; the moisture content of the dewatering is about 70 wt%, and the wet solid residue is self-unloading into the material.
  • the silo the concentrated brine separated from the concentrated floc, has an oil content of 50 mg/L, and the concentrated brine flows into the concentrated brine storage tank and is reused for the hydrolysis reactor.
  • the wet solid residue in the silo is sent to a thin layer drying machine (ie, a drying device) through a stainless steel screw conveyor to form a dry solid residue having a water content of about 15 wt%.
  • the dry solid residue has a sodium chloride content of about 55 wt%, an aluminum hydroxide content of about 22 wt%, a copper hydroxide content of about 7 wt%, and an oil content of less than 1 wt%, which can be used as a general solid waste factory or as a metallurgy.
  • Raw material utilization is used as a general solid waste factory or as a metallurgy.
  • the CODcr produced by the drying process of the thin layer dryer is about 500mg/L, almost free of oil and salt, and flows into the condensate storage tank and is used for the preparation of the lye and flocculant solution.
  • the recovery rate of the acid-soluble oil in the spent catalyst is about 90%; in addition, the water content of the acid-soluble oil recovered is about 1% by weight, and no carbon particle impurities are detected, and the oil is recovered. High quality.
  • the system for treating a chloroaluminate ionic liquid spent catalyst and an alkaline wastewater comprising a hydrolysis reactor 1, a neutralization reactor 2, a flocculation sedimentation system, a mechanical dehydration device 4, and a dry
  • the hydrolysis device 1 is for mixing a chloroaluminate ionic liquid spent catalyst with a concentrated brine to carry out a hydrolysis reaction
  • the neutralization reactor 2 is connected to the hydrolysis reactor 1 for the acidic hydrolysis liquid formed by the hydrolysis reaction and The lye mixture containing the alkaline wastewater is mixed to carry out the neutralization reaction
  • the flocculation sedimentation system is connected with the neutralization reactor 2, and is used for thoroughly mixing the neutralization liquid formed by the neutralization reaction with the flocculating agent and performing sedimentation separation
  • the mechanical dehydration device 4 and The flocculation and sedimentation system is connected for dehydrating the concentrated flocs formed by the sedimentation separation
  • the drying device 5 is connected with the mechanical dewatering device 4 for drying the wet solid
  • the system of the present invention sets the chloroaluminate ionic liquid spent catalyst and the concentrated brine in the hydrolysis reactor 1 by separately providing the hydrolysis reactor 1 and the neutralization reactor 2, respectively, before the neutralization reaction of the spent catalyst with the alkali solution.
  • the hydrolysis is carried out in a mixed reaction; in the hydrolysis reactor 1, a large amount of concentrated brine can rapidly disperse the heat generated by the hydrolysis reaction during the hydrolysis of the spent catalyst, thereby interrupting the self-acceleration mechanism of the hydrolysis reaction;
  • the concentration of chloride ions increases the concentration of the hydrolyzate and has a certain inhibitory effect on the hydrolysis reaction.
  • the above method can not only gently eliminate the activity of the spent catalyst, but also eliminate the promotion effect of the heat of neutralization reaction on the hydrolysis reaction rate, and make the operation process of the whole system more stable and safe.
  • the system of the present invention can be used in the method of Embodiment 1 or Embodiment 2; the structure of each component of the system of the present invention will be described in detail below.
  • the hydrolysis reactor 1 is configured as a flat push flow packed bed reactor which is capable of making the hydrolysis reaction milder, thereby achieving mild hydrolysis; at this time, the spent catalyst and concentrated brine are pushed in the hydrolysis reactor 1 The flow state is contacted, the backmixing degree of the material is low, the disturbance to the waste catalyst droplet is small, the mass transfer between the active component and the moisture is weakened, not only reduces the strength of the hydrolysis reaction, but also facilitates the separation of the acid-soluble oil. With recycling.
  • the structured packing is filled in the flat-flow packed bed reactor, which utilizes the high viscosity characteristics of the spent catalyst, the boundary layer characteristics on the surface of the filler, and the retention of the catalyst by the filler; due to the high viscosity of the spent catalyst,
  • the feed amount is small, and it flows in a laminar flow on the surface of the structured packing, and forms a thick laminar boundary layer.
  • the large viscous force makes the sedimentation rate of the spent catalyst be effectively controlled.
  • the mass transfer resistance between the materials increases, so the mass transfer efficiency between the spent catalyst and the concentrated brine is also effectively controlled.
  • the material circulation hole of the structured packing is uniform, and the channeling phenomenon is not easy to occur.
  • the spent catalyst is evenly distributed in the pores of the structured packing, forming a large number of micro-element reaction environments, and the contact time of the large amount of concentrated brine with the spent catalyst is long, thereby ensuring complete hydrolysis of the spent catalyst.
  • the structured packing has a porosity of 0.95-0.97 m 3 /m 3 and a specific surface area of 300-500 m 2 /m 3 ; at this time, the rate of the hydrolysis reaction is well controlled, which is not easy to cause pore blockage, and the hydrolysis reaction is easy. Completely.
  • the structured packing may be an oleophobic filler and may have a sloping plate structure; the structured packing may also promote coarse granulation of the acid-soluble oil droplets, so that the large-particle oil droplets are more easily floated, thereby facilitating the recovery of the acid-soluble oil.
  • the specific structure and material of the structured packing are not strictly limited; the structured packing can be, for example, a Y-shaped corrugated orifice structured packing, and the inclination angle of the corrugation and the axis can be about 45°, so that the intercepting effect on the waste catalyst droplets is good. .
  • the structured packing material may be polyethylene (PE), polyvinyl chloride (PVC) or polyvinylidene fluoride (PVDF), which is oleophobic and resistant to acid and chlorine, which is favorable for coarse granulation of acid-soluble oil, thereby It is convenient for acid-soluble oil recovery.
  • PE polyethylene
  • PVC polyvinyl chloride
  • PVDF polyvinylidene fluoride
  • the above-described flat-push packed bed reactor may have a space velocity of 0.25-0.5 h -1 .
  • the space velocity is 0.5h -1
  • the spent catalyst can be completely hydrolyzed, and the pH can be stabilized at 2.5-2.8
  • the space velocity is 0.25h -1
  • the acid hydrolyzate has the lowest oil content and the recovered acid-soluble oil is the most. .
  • the hydrolysis reactor 1 includes a casing 11 in which an annular oil collecting groove 12, a water distributor 13 for distributing concentrated brine, and a distribution are arranged in order from the top to the bottom of the casing 11.
  • the distributor 14 of the chloroaluminate ionic liquid spent catalyst is provided with a filler carrier 15 for supporting the filler at the lower portion of the casing 11, and an exhaust port 16 at the top of the casing 11, on the side of the casing 11.
  • the wall is provided with an oil discharge port 17, a water inlet 18 and a feed port 19, the oil discharge port 17 communicates with the annular oil collecting groove 12, the water inlet 18 communicates with the water distributor 13, and the feed port 19 communicates with the distributor 14, in the shell
  • a liquid outlet 110 is provided at the bottom of the body 11.
  • the above structured packing is filled on the packing carrier 15 (see FIG. 4) to form the packing layer 112; in addition, a weir 111 may be disposed above the annular sump 12 to maintain the oil layer and The acid-soluble oil overflows evenly.
  • the spent catalyst in view of the extremely strong acidity of the spent catalyst, and the viscosity of up to 600-800 mPa ⁇ s, and containing a small amount of mechanical impurities, in order to prevent clogging and corrosion, it is preferably transported by a mechanical diaphragm pump 71 of a fluoroplastic material;
  • the sodium chloride content in the concentrated brine is as high as 15-22% by weight, and is highly corrosive, and is preferably conveyed by a centrifugal pump 72 made of stainless steel.
  • the spent catalyst is mixed with concentrated brine to carry out a hydrolysis reaction, and the acid-soluble hydrocarbon in the spent catalyst is separated from the active component, and the formed acid-soluble oil is floated to the liquid surface, and collected by the annular oil collection tank 12, and then The oil discharge port 17 and its piping flow into the dirty oil storage tank 67 for refining (see Fig. 5).
  • the water inlet 18 and the water distributor 13 are respectively disposed above the feed port 19 and the distributor 14, which is advantageous not only for the dispersion of the spent catalyst by the concentrated brine but also for the waste catalyst.
  • the area where the hydrolysis reaction takes place is far away from the acid-soluble oil layer, and the influence of the local exothermic heat of hydrolysis on the quality and recovery rate of the acid-soluble oil is avoided.
  • the active component and the acid-soluble hydrocarbon contained in the spent catalyst generate volatile organic pollutants (VOCs) and hydrogen chloride during the hydrolysis process, which are concentrated at the top of the hydrolysis reactor 1, in order to avoid contamination of the air,
  • VOCs volatile organic pollutants
  • An exhaust port 16 is provided at the top of the hydrolysis reactor 1, and the gas is led to the water seal of the brine storage tank 62.
  • the concentrated brine in the brine storage tank 62 can absorb these gaseous pollutants, and can also utilize the liquid level.
  • the water seal is carried out; the water seal can also provide a positive pressure to the hydrolysis reactor 1 to promote the reabsorption of these contaminants by the acidic hydrolyzate.
  • the structure of the water distributor 13 and the distributor 14 of the hydrolysis reactor 1 is not strictly limited as long as it can uniformly distribute the concentrated brine and the spent catalyst to the hydrolysis reactor 1.
  • the water distributor 13 includes a water distribution pipe 101 , and a plurality of water distribution pipes 102 arranged in parallel and equally spaced are respectively disposed on two sides of the water distribution pipe 101.
  • a plurality of water distribution holes are disposed at the bottom of each water distribution pipe 102, and the total opening area of the water distribution holes accounts for more than 1% of the cross-sectional area of the hydrolysis reactor 1.
  • the water distributor 13 is of the fishbone type; wherein the spacing between the adjacent water distribution pipes 102 can be set to be 5 cm or more, thereby avoiding affecting the floating and collecting of the acid-soluble oil; moreover, the cloth on the water distribution pipe 102
  • the arrangement of the water holes is not strictly limited, and the plurality of water holes may be equally spaced, and the apertures of the plurality of water holes may be set to be the same.
  • the water distributor 13 having the above structure has a large opening area and a large number of openings, thereby facilitating the uniform distribution of the concentrated brine; in addition, since the flow velocity of the water outlet hole is small and the back mixing is low, the hydrolysis reactor 1 is The laminar flow is formed, the mass transfer between the spent catalyst and the spent catalyst is weakened, and the acid-soluble oil layer on the hydrolyzed liquid surface is less disturbed, which is more favorable for the recovery of the acid-soluble oil.
  • the distributor 14 includes a cloth main pipe 201, and a plurality of concentric and equally spaced semicircular cloth branch pipes 202 are respectively disposed on both sides of the cloth main pipe 201.
  • a plurality of cloth holes 203 are distributed at the bottom of the half circular cloth branch pipe 202, and the total opening area of the cloth holes 203 accounts for more than 2% of the cross-sectional area of the hydrolysis reactor 1.
  • the distributor 14 is of a ring type; wherein the spacing between the adjacent cloth branch pipes 202 can be set to be 5 cm or more, thereby avoiding affecting the floating and collecting of the acid-soluble oil; moreover, the cloth holes 203 on the cloth branch pipe 202
  • the arrangement manner is not strictly limited, and the plurality of cloth holes 203 may be disposed at equal intervals, and the apertures of the plurality of cloth holes 203 may be set to be the same, and the inner diameter of the cloth holes 203 may be set to, for example, 3-5 mm.
  • the hopper 14 having the above structure has a large opening area and a large number of cloth holes, thereby facilitating uniformity of the waste catalyst cloth; moreover, since the inner diameter of the cloth hole 203 is small, the spent catalyst is extruded as small droplets, which is more advantageous for Dispersion in concentrated brine.
  • the neutralization reactor 2 is used for mixing the acidic hydrolyzate formed by the hydrolysis reaction with the alkali solution containing the alkaline waste water for neutralization reaction; the specific structure of the neutralization reactor 2 is not strictly limited, and the conventional neutralization in the art can be employed. reactor.
  • the neutralization reactor 2 is provided as a full mixed flow reactor; as shown in FIG. 9, the neutralization reactor 2 includes a casing 21, and a cloth for distributing lye is provided in order from the top to the bottom of the casing 21
  • the water tank 22 and the distributor 23 for distributing the neutralizing liquid are provided with a side-in type agitator 24 in the middle of the casing 21, and an exhaust port 25 at the top of the casing 21, on the side wall of the casing 21.
  • the inlet port 26 and the inlet port 27 are provided, the inlet port 26 is in communication with the water distributor 22, the inlet port 27 is in communication with the distributor 23, and the outlet port 28 is provided at the bottom of the casing 21.
  • the inlet port 26 and the water distributor 22 of the neutralization reactor 2 are disposed above the inlet port 27 and the distributor 23, so that the position of the metal hydroxide flocs generated by the neutralization reaction can be made low, thereby being less likely to clog.
  • Water distributor 22 In particular, the use of the side-feeding agitator 24 accelerates the mass transfer and neutralization reaction between the acidic hydrolyzate and the lye, and also prevents premature precipitation of the flocs to block the liquid outlet 28 and its piping.
  • the high-chlorine-containing acidic hydrolyzate can be transported by using a centrifugal pump 77 of fluoroplastic material; the alkali-washing wastewater and the exogenous alkali liquid are high in chlorine and high in alkali, and need to be accurately matched with the acidic hydrolyzate to achieve Neutralization is therefore preferred for the use of a metering pump 73, 74 of fluoroplastic material for transporting the alkaline washing wastewater and the exogenous lye.
  • the neutralization process causes enrichment of VOCs at the top of the neutralization reactor 2; to prevent air pollution, an exhaust gas may be provided at the top of the neutralization reactor 2. Port 25, and the gas is led to the water seal of the concentrated brine storage tank 62.
  • the concentrated brine in the concentrated brine storage tank 62 can absorb these gaseous pollutants or use the liquid level for water sealing; the water seal can also be neutralized.
  • Reactor 2 provides a positive pressure to promote the reabsorption of these contaminants by the neutralizing liquid.
  • the structure of the water distributor 22 and the distributor 23 of the neutralization reactor 2 is not strictly limited, and as long as the alkali liquid and the acidic hydrolyzate can be uniformly distributed in the neutralization reactor 2, it can be used in the hydrolysis reactor 1.
  • the outer alkaline solution is uniformly distributed in the neutralization reactor 2; further, the acidic hydrolyzate is dispensed in the neutralization reactor 2 via the above-mentioned ring type distributor 23, and the distributor 23 has a small opening area and a cloth opening. The amount is small, the inner diameter is small, and local turbulence is formed after the liquid is discharged, which contributes to the mass transfer and neutralization reaction between the acidic hydrolyzate and the lye.
  • the flocculation sedimentation system is used to thoroughly mix the neutralized liquid generated by the neutralization reaction with the flocculant and carry out sedimentation separation; the specific structure of the flocculation sedimentation system is not strictly limited, and a structure conventional in the art can be employed.
  • the flocculation sedimentation system includes a pipeline mixer 8 and a flocculation sedimentation device 3 arranged in sequence; as shown in FIG. 10, the flocculation sedimentation device 3 includes a sealed casing 31, and an annular overflow weir 32 is disposed inside the sealed casing 31,
  • the center tube 33 and the cloth tube 34 are disposed inside the center tube 33, and an umbrella-shaped baffle 35 is provided at the bottom of the center tube 33, and an exhaust port 36 is provided at the top of the seal housing 31.
  • the side wall of the body 31 is provided with a water outlet 37 and a feed port 38.
  • the water outlet 37 communicates with the annular overflow weir 32.
  • the feed port 38 communicates with the cloth pipe 34, and a slag opening 39 is provided at the bottom of the sealed casing 31. .
  • the liquid outlet 28 of the neutralization reactor 2 is connected to the inlet of the pipeline mixer 8 via a pipeline, and the addition pipeline is provided on the connection line of the inlet 2 of the neutralization reactor 2 and the inlet of the pipeline mixer 8.
  • the outlet of the flocculant preparation tank 65 is connected to the metering pump 75 of stainless steel and the pipeline and the addition port.
  • the pipe mixer 8 facilitates sufficient contact between the neutralizing liquid and the flocculating agent; in addition, the dosing pump 75 of stainless steel is used for the dosing, so that the flocculating agent and the neutralizing liquid are accurately matched to achieve the most Excellent flocculation effect.
  • the flocculation and sedimentation device 3 having the above structure is in the form of a sealed vertical flow type sedimentation tank; the neutralization liquid containing the flocs is thoroughly mixed with the flocculant through the pipeline mixer 8, and is subjected to self-flow into the flocculation and sedimentation device 3 for sedimentation and separation, and the flocculation is carried out.
  • the water content of the body is lowered, the processing load of the subsequent mechanical dehydration device 4 is alleviated, and the precipitated concentrated brine can be reused for the hydrolysis reactor 1. Since the material in the flocculation and sedimentation device 3 is likely to escape gaseous pollutants, a sealed form is employed while the exhaust port 36 provided at the top thereof directs the gas to the brine storage tank 62 for water sealing.
  • the flocculation and sedimentation device 3 in the form of the vertical flow sedimentation tank is used to separate the concentrated brine from the flocs; the neutralization liquid is mixed with the flocculant and then passed through the feed port. 38 enters the flocculation and sedimentation device 3, the cloth pipe 34 drives the neutralizing liquid downward into the central pipe 33, and is deflected by the umbrella baffle 35, and the metal hydroxide flocs are precipitated and concentrated toward the bottom of the flocculation and sedimentation device 3; The brine is lifted to the top of the flocculation and sedimentation device 3 and flows into the brine storage tank 62 via the annular overflow weir 32 and the water outlet 37. When a certain sedimentation time is reached, the interface between the concentrated floc and the concentrated brine is clear, and the concentrated brine is almost free of flocculation.
  • the mechanical dewatering device 4 is used for dehydrating the concentrated flocs, thereby significantly reducing the amount of solid residue; since the concentrated floc has a solid content of about 2-3 wt% and contains concentrated brine, the stainless steel screw pump 78 can be used. delivery.
  • the water in the concentrated flocs is mainly free water, so a good dewatering effect can be obtained by using a conventional plate and frame filter press or a centrifugal dewatering machine. Since the plate and frame filter press has the disadvantages of large land occupation, long processing time, and inability to continuously operate, the mechanical dewatering device 4 is preferably a centrifugal dewatering machine, and the separation factor can be about 3000, and the concentrated floc can be prepared at this time.
  • the moisture content is 60-70% moisture.
  • the drying device 5 is used for drying the wet solid residue formed by the mechanical dehydration treatment, thereby continuing to reduce the solid residue production and facilitating reuse.
  • the screw conveyor 9 can be used to transport the wet solid residue; the conveying method is relatively clean, and the phenomenon of slag dropping in the belt transmission is avoided.
  • the moisture in the above-mentioned wet solid residue is mainly capillary water, and it is difficult to continuously reduce the water content and the solid residue production by the plate frame pressure filtration or the centrifugal dewatering method, and the drying method is more suitable for drying and dehumidifying. Therefore, the drying device 5 can employ a thin layer drying machine or a low temperature dehumidifying drying machine which can dry the wet solid residue into a dry solid residue having a water content of 10-20%.
  • the thin-layer drying machine is coupled with the principle of conduction and radiation drying.
  • the indirect heating method of hot fluid is adopted, which has a high vaporization rate of moisture in the wet solid residue, but the energy consumption and equipment investment are high; the low-temperature dehumidifying and drying machine is based on convection.
  • the drying principle is generally based on electric direct heating. The speed of gasification and dehumidification is slower than that of thin layer drying. However, the equipment investment is low and the process operation is simple.
  • a thin layer dryer is preferably employed. Since the moisture in the dry slag is mainly crystallization water, it is not only inefficient and uneconomical to continue to lower the water content.
  • the system of the present invention may further include a heat recovery device (ie, condensate storage tank 6666) for recovering the condensed water produced by the above-described drying device 5; since the recovered condensed water has a low pollution load, it can be reused Preparation of exogenous alkali liquor and flocculant.
  • a heat recovery device ie, condensate storage tank 6666
  • the system of the present invention includes other supporting components in addition to the above-mentioned main body components, including a spent catalyst storage tank 61, a brine storage tank 62, an alkaline washing wastewater storage tank 63, and an external lye preparation tank. 64.
  • the spent catalyst storage tank 61 comprises a tank body, and a side-feeding agitator is arranged inside the tank body, a feeding port and a discharging port are arranged at a lower end of the tank body side, and an air discharging port is arranged at the bottom of the tank body.
  • a gas inlet 611 is disposed at the top of the tank; wherein the side-feeding agitator is used for homogeneously equalizing the spent catalyst from different time periods, and the gas inlet 611 is used for protecting the top of the spent catalyst storage tank 61 with nitrogen gas. To prevent the spent catalyst from coming into contact with moisture in the air to prevent the hydrolysis from exploding.
  • the concentrated brine storage tank 62 comprises a tank body and a water sealing tube, and a water inlet is arranged at an upper end of the side wall of the tank body, a water outlet is arranged at a lower end of the side wall of the tank body, and an air outlet is arranged at the bottom of the tank body, and the top of the tank body is provided at the top of the tank body.
  • the concentrated brine storage tank 62 provides space for the storage of the concentrated brine of the intermediate product, and provides the raw material for the hydrolysis reaction, and is a key node for recycling the intermediate product of the whole system; meanwhile, the hydrolysis reactor can be controlled by the water seal. The escape of gaseous pollutants in the reactor and the flocculation and sedimentation device avoids air pollution.
  • the alkaline washing wastewater storage tank 63 includes a tank body, and a side-feeding agitator is arranged inside the tank body, and a water inlet and a water outlet are arranged at a lower end of the tank body side, and an air outlet is arranged at the bottom of the tank body;
  • the agitator is used to homogenize the alkaline washing wastewater from different time periods.
  • the condensed water storage tank 66 comprises a tank body, and a water inlet is arranged at an upper end of the side wall of the tank body, a condensed water outlet is arranged at a lower end of the side wall of the tank body, and an air outlet is provided at the bottom of the tank body.
  • the condensate storage tank 66 provides space for the storage of intermediate product condensate, and provides a water source for the preparation of the external lye and flocculant, and is an important node for recycling the intermediate products of the whole system.
  • the spent catalyst storage tank 61 is connected to the feed port 19 of the hydrolysis reactor 1 through a mechanical diaphragm pump 71, and the brine storage tank 62 is connected to the water inlet 18 of the hydrolysis reactor 1 through a centrifugal pump 72, and the hydrolysis reactor 1 is
  • the oil discharge port 17 is connected to the oil storage tank 67.
  • liquid outlet 110 of the hydrolysis reactor 1 is connected to the liquid inlet 27 of the neutralization reactor 2 by a centrifugal pump 77, and the alkali washing wastewater storage tank 63 and the external alkali liquid preparation tank 64 are respectively passed through the metering pumps 73, 74. It is connected to the inlet port 26 of the neutralization reactor 2, and the outlet port 28 of the neutralization reactor 2 is connected to the inlet of the pipe mixer 8.
  • outlet of the pipe mixer 8 is connected to the feed port 38 of the flocculation and sedimentation device 3, and the slag port 39 of the flocculation and sedimentation device 3 is connected to the inlet of the mechanical dewatering device 4 by a screw pump 78.
  • the slag discharge port of the mechanical dewatering device 4 is connected to the silo 10; the silo 10 is connected to the inlet of the drying device 5 through the screw conveyor 9; in addition, the condensate storage tank 66 is connected to the drying device 5 to recover the condensation. water.
  • the condensate storage tank 66 is also connected to the water inlet of the external lye preparation tank 64 and the water inlet of the flocculant preparation tank 65 by a metering pump 76.
  • the exhaust port 16 of the hydrolysis reactor 1, the exhaust port 25 of the neutralization reactor 2, the water outlet 37 of the flocculation and sedimentation device, and the exhaust port 36 are respectively connected to the water seal of the brine storage tank 62 through a pipeline. .
  • the flocculation and sedimentation device 3 and the mechanical dewatering device 4 have a concentrated brine outlet, and the brine outlet is connected to the brine storage tank 62 to facilitate reuse of the concentrated brine.
  • the system of the present invention utilizes the hydrolysis reactor 1 and the neutralization reactor 2 to realize the detoxification of the spent catalyst and the alkaline washing wastewater and the recovery of the oil resources, and is realized by the flocculation sedimentation system, the mechanical dewatering device 4 and the drying device 5.
  • the reduction and recycling of the metal slag; in addition, the recycling of the intermediate product is achieved by the brine storage tank 62 and the condensate storage tank 66.
  • the operation of the whole system is mild, the operation process is safe, there is no new pollution source, and the recovery rate of resources is high, especially the recovered acid-soluble oil has low content of water and impurities, and the quality of the oil is high.

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Abstract

一种处理氯铝酸类离子液体废催化剂和碱性废水的方法和系统。该方法包括：1)将氯铝酸类离子液体废催化剂与浓盐水混合进行水解反应，至废催化剂的残留活性完全消除，得到酸性水解液和酸溶油；2)将酸性水解液与包含碱性废水的碱液混合进行中和反应，至反应体系为弱碱性，得到含有金属氢氧化物絮体的中和液；3)将中和液与絮凝剂充分混合并实施沉降分离，收取上层的浓盐水回用于水解反应，同时收取下层的浓缩絮体；4)对浓缩絮体进行脱水处理，收取湿固渣，并将脱出的浓盐水回用于水解反应；5)对湿固渣进行干燥处理，得到干化固渣。上述方法能够温和地消除废催化剂的活性，工艺操作的稳定性和安全性好，回收油品的品质高。

Description

处理氯铝酸类离子液体废催化剂和碱性废水的方法和系统 技术领域
本发明属于石油化工技术领域，具体涉及一种处理氯铝酸类离子液体废催化剂和碱性废水的方法和系统。
背景技术
随着国家清洁油品升级战略进入加速推进期，作为理想的清洁汽油调和组分，高辛烷值烷基化油的需求迎来了爆发式的增长。以C4为原料催化烷基化是生产烷基化油的主要工艺，现有的烷基化工艺大多采用氢氟酸法和硫酸法两条传统工艺路线。然而，上述传统工艺路线采用氢氟酸和硫酸作为催化剂，不仅给工艺、设备以及人员造成了巨大的安全隐患，此外工艺过程排放的大量“废酸渣”及含碱废水也构成了重大的环境隐患。即使以高投入对“废酸渣”进行再生处理，烟气SO 2、NO x和酸雾含量也不能满足环保标准。因此，烷基化油的生产急需更为安全环保的先进工艺。
以离子液体作为烷基化反应的催化剂，在产品转化效率、过程安全性以及环境友好性上要远优于传统的氢氟酸法和硫酸法。与氢氟酸法和硫酸法相比，氯铝酸类离子液体烷基化工艺整体竞争力较强，目前已经被新建的烷基化油生产装置所采用。然而，氯铝酸类离子液体烷基化工艺仍然会产生少量的废催化剂和碱性废水(即碱洗废水)，其中每吨烷基化油副产废催化剂3kg左右、碱洗废水20-30kg，产量分别为硫酸法的5％和3％。氯铝酸类离子液体烷基化工艺产生的废催化剂与新催化剂的组分基本相同，只是活性略有降低，并且含有酸溶性烃，因此具有高活性、高酸性以及高含油等特性，对其进行无害化和资源化处置极为必要。
公开号为CN 105457973 A的发明专利公开了一种对氯铝酸类离子液体废催化剂进行处理的方法及系统，其先将废催化剂与碱溶液进行消解-中和反应从而消除废催化剂的活性与酸性，随后再对废催化剂中的金属和油类资源进行回收。上述方法及系统能够在一定程度上对氯铝酸类离子液体废催化剂进行无害化处理并实现废催化剂中金属和酸溶油的资源化，然而本发明人经大量研究发现，上述方法及系统仍存在以下缺陷：1)在消解反应器中直接加 碱对废催化剂进行消解-中和，反应过程非常剧烈，工艺及系统的稳定性与安全性相对较差；2)废催化剂中的酸溶油在消解-中和反应过程中易造成碳化，酸溶油的回收率低于70％，此外回收得到的酸溶油的含水率高(含水率为7wt％左右)，并且存在颗粒碳杂质(颗粒碳杂质的含量为5wt％左右)，油品的品质较差；3)对废催化剂进行消解-中和得到的是由水相/酸溶油相/絮体组成的三相混合物，在回收酸溶油时需要对乳化油进行破乳收油，不利于后续处理；4)采用两次絮凝及两次脱水方式回收废催化剂中的金属和酸溶油，工艺相对复杂，操作成本较高。
此外，氯铝酸类离子液体烷基化工艺中，对烷基化油产品进行碱洗是保障油品质量的重要措施，所排放的碱洗废水中通常含有氢氧化钠、偏铝酸钠、氯化钠以及少量的石油类污染物。目前，通常将该碱洗废水排到污水处理系统进行处理，不仅需要投加大量的外源酸类对其进行中和，并且中和后会新增大量的含氢氧化铝物化污泥，中和后废水的盐负荷和有机负荷较高，对污水处理系统的稳定运行构成严重冲击。
由于氯铝酸类离子液体烷基化是石油化工领域的新工艺，对于废催化剂和碱洗废水这两类新型污染源的处理方式尚在不断的探索之中。因此，如何对氯铝酸类离子液体废催化剂和碱洗废水这两类污染源进行无害化、资源化的处理和利用，从而实现氯铝酸类离子液体烷基化工艺的绿色升级，是石油化工领域面临的重大问题。
发明内容
本发明提供一种处理氯铝酸类离子液体废催化剂和碱性废水的方法和系统，该方法和系统能够克服上述现有技术存在的缺陷，不仅能够温和地消除废催化剂的活性，工艺操作的稳定性和安全性好，此外废催化剂中的酸溶油不易碳化，酸溶油的回收率高，回收得到的酸溶油中水及杂质的含量低，油品的品质高。
本发明提供一种处理氯铝酸类离子液体废催化剂和碱性废水的方法，包括如下步骤：
1)将氯铝酸类离子液体废催化剂与浓盐水混合进行水解反应，至氯铝酸类离子液体废催化剂的残留活性完全消除，对水解反应产物进行分离，分别 得到酸性水解液和酸溶油；
2)将所述酸性水解液与包含碱性废水的碱液混合进行中和反应，至反应体系为弱碱性，得到含有金属氢氧化物絮体的中和液；
3)将所述中和液与絮凝剂充分混合并实施沉降分离，收取上层的浓盐水回用于所述水解反应，同时收取下层的浓缩絮体；
4)对所述浓缩絮体进行脱水处理，收取湿固渣，并将脱出的浓盐水回用于所述水解反应；
5)对所述湿固渣进行干燥处理，得到干化固渣。
本发明对氯铝酸类离子液体废催化剂(以下简称为废催化剂)不作严格限制，例如可以来自利用氯铝酸类离子液体催化C4烃的烷基化反应、利用氯铝酸类离子液体催化烯烃的聚合反应、催化Friedel-Crafts烷基化反应或Friedel-Crafts酰基化反应产生的废催化剂。
在本发明的具体方案中，氯铝酸类离子液体废催化剂为利用氯铝酸类离子液体催化碳四生产烷基化油产生的废催化剂；该氯铝酸类离子液体废催化剂的黏度达600-800mPa·s，活性组分主要为氯化铝、氯化铜等，其他组分主要为酸溶性烃(即酸溶油)。
本发明人经研究发现，上述现有技术直接加碱对废催化剂进行消解-中和会导致反应过程非常剧烈，其原因可能在于：氯铝酸类离子液体废催化剂的主要活性组分是氯化铝，其水解反应速率较高，在与水接触后会迅速水解生成氯化氢而使水解液呈强酸性；同时，水解反应放热增大了水解反应速率常数，进一步提高了氯化铝的水解反应速率。特别是，在氯化铝水解过程中直接加入强碱，强碱与氯化氢的中和反应会释放大量的热，进一步增加了氯化铝的水解反应速率；如不能及时散热，瞬时剧烈的放热会形成局部高温，从而造成酸溶油的碳化以及油烟、氯化氢酸雾的生成，此外还存在爆炸的风险。
因此，本发明在采用碱液对废催化剂进行中和反应之前，先将氯铝酸类离子液体废催化剂与浓盐水混合进行水解反应；研究发现，大量的浓盐水在废催化剂的水解过程中能够将水解反应产生的热快速分散，从而将水解反应的自加速机制打断；同时，浓盐水中高浓度的氯离子增加了水解产物的浓度，对水解反应具有一定的抑制作用。上述方式不仅能够温和地消除废催化剂的活性，同时能够消除中和反应热对水解反应速率的促进作用，使工艺操作更 加稳定和安全；鉴于此，从而完成了本发明。
在本发明的步骤1)中，水解反应主要用于将氯铝酸类离子液体废催化剂的残留活性完全消除；具体地，在残留活性完全消除时，酸溶油实现最大可能地被分离，酸性水解液的pH值一般会稳定在2.5-2.8，即为水解反应终点。
特别是，步骤1)中，所述浓盐水中氯化钠的含量可以为15-22wt％；此外，所述氯铝酸类离子液体废催化剂与浓盐水的进料体积比可以为1：(50-60)。
研究发现：浓盐水与废催化剂的进料体积比越大，废催化剂的水解反应越温和；当浓盐水与废催化剂的进料体积比低于50：1时，水解反应体系的温升变得明显，并有氯化氢酸雾逸出；当浓盐水与废催化剂的投料体积比低于10：1时，开始出现酸溶油的碳化并有油烟产生。鉴于浓盐水与废催化剂的进料体积比过大时所需的反应器体积过大，因此可以将氯铝酸类离子液体废催化剂与浓盐水的进料体积比设置为1：(50-60)。
此外，浓盐水中氯化钠的质量含量越高，废催化剂的水解反应越温和；然而，当浓盐水中氯化钠的含量高于22wt％时，会使水解液中氯离子的浓度过高从而导致氯化钠结晶析出；当浓盐水中氯化钠的含量低于15wt％时，水解反应体系的温升变得明显。因此，可以将所述浓盐水中氯化钠的含量设置为15-22wt％。
在上述条件下，整个水解反应体系的升温不明显，并且未出现酸溶油碳化以及明显的酸雾逸出现象，水解反应较为温和。
进一步地，本发明人经研究发现，现有技术采用全混流反应器进行消解-中和反应会导致酸溶油碳化从而回收率较低，其原因可能在于：废催化剂的黏度较高，其在浓盐水中以液滴的形态出现，在废催化剂的水解反应过程中，活性组分与水分之间的传质是控制因素；由于废催化剂中酸溶性烃对活性组分的包覆，使得活性组分与水分之间的传质被削弱，其有利于水解反应的温和进行。然而，如果使废催化剂液滴与水体之间以全混流状态进行接触，会加速酸溶性烃与活性组分的分离，活性组分与水体之间的传质被强化，水解反应速率被提高，水解反应过程会更加剧烈；同时，生成的酸溶油还会被裹挟进反应体系中，既容易造成碳化，此外降低了酸溶油的回收率。因此，在 水解反应阶段使物料温和接触和反应，尽可能降低物料返混是有利的。
本发明的实施方案是在平推流填充床反应器中进行上述水解反应，以便使水解反应更加温和(即实现温和水解)；此时，废催化剂与浓盐水以平推流状态进行接触，物料的返混程度低，对废催化剂液滴的扰动小，活性组分与水分之间的传质被弱化，不仅降低了水解反应的强度，而且有利于酸溶油的分离与回收。
鉴于废催化剂的密度约为1.36kg/L，酸性水解液和浓盐水的密度一般不超过1.2kg/L；此时，废催化剂液滴在浓盐水中的沉降速度较快，不利于废催化剂的完全水解。因此，本发明在平推流填充床反应器中填充规整填料，该方式综合利用了废催化剂的高黏度特性、在填料表面的边界层特性以及填料对催化剂的截留作用；由于废催化剂的黏度高、进料量小，其在规整填料表面呈膜状的层流流动，并形成较厚的层流边界层，较大的黏性力使废催化剂的沉降速率被有效控制。此外，由于边界层内层流底层的存在，物料间的传质阻力增大，因此废催化剂与浓盐水之间的传质效率也被有效控制。相对于散堆填料，规整填料的物料流通孔道均匀，不易出现沟流现象。
特别是，通过采用高通量的规整填料，能为浓盐水提供通畅的流路，并基本保持层流状态，同时能减弱与废催化剂之间的传质。在进行水解反应时，废催化剂在规整填料的孔隙中均匀分布，形成数量众多的微元反应环境，大体量的浓盐水与废催化剂的接触时间长，从而保证了对废催化剂的彻底水解。
研究发现：规整填料的孔隙度和比表面积对水解反应的影响较大；孔隙度过低或比表面积过大时，存在酸溶油和杂质堵塞填料孔道的风险；孔隙度过高或比表面积过小时，对废催化剂的截留作用减弱，存在水解反应不完全的风险。规整填料的孔隙度在0.95-0.97m 3/m 3(即每m 3规整填料的孔隙体积为0.95-0.97m 3)、比表面积在300-500m 2/m 3(即每m 3规整填料的比表面积为300-500m 2)之间时，水解反应的速率控制较好，既不易造成孔道堵塞，同时水解反应易完全进行。
进一步地，规整填料可以为疏油性填料并且可以具有斜板结构；该规整填料还能够促进对酸溶油滴的粗粒化，使大颗粒油滴更容易上浮，从而有利于酸溶油的回收。
对规整填料的具体结构及材质不作严格限制；规整填料例如可以为Y型 波纹孔板规整填料等，其波纹与轴线的倾角可以为45°左右，从而对废催化剂液滴的截留效果好。此外，规整填料的材质可以为聚乙烯(PE)、聚氯乙烯(PVC)或聚偏氟乙烯(PVDF)，其具有疏油性且耐酸耐氯腐蚀，有利于酸溶油的粗粒化，从而便于酸溶油回收。
进一步地，使用上述平推流填充床反应器实施水解反应时，空速可以为0.25-0.5h -1。其中，当空速为0.5h -1时，利于废催化剂完全水解，pH值能够稳定在2.5-2.8；当空速为0.25h -1时，酸性水解液的含油量最低，回收得到的酸溶油可达到最多。
在废催化剂与浓盐水的温和水解反应完成后，废催化剂中的氯化铝等活性组分完全失活，最终进入到酸性水解液中；废催化剂中的酸溶油经沉降等常规方式即可进行回收及再利用。水解反应形成的酸性水解液中的氯化钠含量高、酸性较强且含有金属资源，后续可对其进行中和处理以实现无害化和资源化。
在本发明的步骤2)中，可以利用碱性废水对水解反应形成的酸性水解液进行中和反应；本发明对碱性废水不作严格限制，例如可以为利用氯铝酸类离子液体催化碳四生产烷基化油产生的碱洗废水，其氢氧化钠含量为10-15wt％左右。上述方式通过“以废治废”实现了对废催化剂和碱性废水的同步联合处理，既降低了外源酸、碱的投加量，同时避免了碱洗废水对污水处理系统的冲击。
酸性水解液经碱液中和后的弱碱性中和液中主要构成为金属氢氧化物絮体以及浓盐水，控制为弱碱性利于金属氢氧化物絮体尽可能多地形成，比如pH在7.5以上，可观察絮体的形成基本稳定作为中和反应完成的标准。具体操作中，检测中和液的pH值稳定在8.0-8.5，即为中和反应终点。在进行中和反应时，对碱液的浓度不作严格限制，碱液浓度可以根据中和液中氯化钠的浓度进行适宜调节；在碱性废水不足以满足中和反应所需要求时，可以补充外源碱液，此时碱性废水与外源碱性共同构成对酸性水解液进行中和反应的碱液。
具体地，当中和液中氯化钠的浓度低于15wt％时，可以增加碱液的浓度；当中和液中氯化钠的浓度高于22wt％时，可以降低碱液的浓度。对外源碱液的配制浓度不作严格限制，外源碱液中氢氧化钠的含量可以为25-35wt％。
在上述中和反应过程中，酸性水解液中的铝、铜等金属离子与碱液中的氢氧根离子结合形成金属氢氧化物絮体；同时，碱液中的钠离子与酸性水解液中的氯离子形成的高浓度的氯化钠(即浓盐水)，此外酸性水解液中携带的少量油类也转移至中和液中。
在本发明中，中和反应可以在全混流反应器中进行；全混流反应器能够进行快速的中和反应，从而能够减小反应器的体积。特别是，全混流反应器的空速可以为1-2h -1；其中，当全混流反应器的空速达到2h -1时，利于酸性水解液完全中和，中和液的pH值稳定在8.0-8.5，即为中和反应终点；当空速增加到1h -1时，中和液中的金属氢氧化物絮体的产量最高，金属氢氧化物絮体的含量达到2.5-3wt％。
经上述中和反应形成的中和液的主要构成为金属氢氧化物絮体以及浓盐水，后续采用絮凝剂进行沉降分离，即可对金属氢氧化物絮体和浓盐水进行初步分离。收取的浓盐水可回收用于废催化剂的水解反应；金属氢氧化物絮体沉淀浓缩后体积减小，降低了后续脱水处理的负荷。
在本发明的步骤3)中，向中和液中加入絮凝剂，可以通过吸附架桥作用，将松散的小颗粒金属氢氧化物絮体转化为密实的大颗粒絮体(促使颗粒之间相互粘结而成)，更有利于金属氢氧化物絮体的沉淀。对中和液与絮凝剂的混合方式不作严格限制，例如可以利用管道混合器进行充分混合，随后利用絮凝沉淀装置进行絮体与浓盐水的沉降分离。
本发明对所采用的絮凝剂不作严格限制，例如可以采用阴离子型聚丙烯酰胺絮凝剂，其更适合于金属氢氧化物絮体的絮凝。具体地，阴离子型聚丙烯酰胺絮凝剂的相对分子量范围可以为600-1800万，进一步为1200-1800万；电荷密度范围可以为10-40％，进一步为10-30％。采用上述阴离子型聚丙烯酰胺絮凝剂更利于促进氢氧化铝、氢氧化铜颗粒之间的相互黏结，从而便于形成更大的絮体。
絮凝剂的使用量以能有效促进絮体的形成与沉降为标准。进一步地，研究发现：在每吨中和液中加入20g以上的上述絮凝剂时，形成的絮体粗大密实，沉降性能好；当每吨中和液中絮凝剂的加入量超过30g时，对絮体沉降性能的提升不大，且在成本上不经济。因此，可以将上述絮凝剂的投加量设置为每吨中和液加入絮凝剂20-30g。
此外，在实施沉降分离时，一般可以观察絮体的沉降不再明显增加为完成标准，生产可以观察发现，当沉降分离时间达到2h左右时，浓缩絮体与浓盐水之间的界面清晰，浓盐水几乎无絮体夹带，浓缩絮体层占中和液体积的25％左右；沉降分离时间在3h以上时，浓缩絮体层沉淀非常彻底，仅占中和液体积的20％，继续增加沉淀时间对于降低浓缩絮体层体积没有贡献。因此，可以将沉降分离的时间设置为2-3小时。
经上述沉降分离后，形成的浓缩絮体中浓盐水的含量可以达到约85-90wt％，金属氢氧化物的固体含量约为10-15wt％。此外，中和液中的少量油分会集中在浓盐水相中，因此浓缩絮体的含油量很低，更为清洁，便于其后续回收利用。
鉴于浓缩絮体中含有大量的浓盐水，其绝对产量较大，将其作为冶金原料或固废外运经济性较差，同时浓盐水为废催化剂水解反应的必需资源。因此，本发明对浓缩絮体进行脱水处理，从而降低金属氢氧化物系统的总量，同时对浓盐水进行返回利用。
在本发明的步骤4)中，对浓缩絮体的脱水处理方式不作严格限制，可以采用常规的机械脱水方式，例如板框压滤或离心脱水等。金属氢氧化物浓缩絮体的颗粒大，所含的水以自由水为主，无论采用压力过滤或离心过滤方式，均能够实现金属氢氧化物固体与浓盐水的分离。其中，采用板框压滤方式进行脱水时，操作压力可以为0.45MPa左右；采用离心方式进行脱水时，离心脱水的分离因数可以为3000左右。经上述脱水处理形成的湿固渣(即金属氢氧化物浓缩絮体)含水率为60-70wt％左右；脱水处理分离形成的浓盐水可回用于上述水解反应。
进一步地，鉴于脱水处理形成的湿固渣中的水分主要为毛细水，无论采用板框压滤还是离心脱水方式均难以继续降低其含水率和固渣产量。因此，在本发明的步骤5)中，可以采用薄层干燥或低温除湿干燥方式对湿固渣进行干燥处理，从而以较低的能耗实现湿固渣中毛细水的去除。
薄层干燥技术耦合了传导和辐射干燥原理，一般采用热流体间接加热方式，其对湿固渣中水分的汽化速度较快；低温除湿干燥技术基于对流干燥原理，一般采用电直接加热方式，气化除湿的速度虽比薄层干燥慢，然而设备投资低，工艺操作简单。在存在余热介质可以利用的情况下，优选薄层干燥 技术。此外，无论采用薄层干燥或低温除湿干燥，均可以通过回收水蒸汽的潜热来降低能耗；在热能回收阶段产生的凝结水的污染程度较轻，可以回用于碱液及絮凝剂溶液的配制。经上述干燥处理形成的干化固渣含水率为10-20wt％。
本发明提供的处理氯铝酸类离子液体废催化剂和碱性废水的方法，主要采用“温和水解-快速中和-絮凝沉淀-机械脱水-除湿干燥”的主体技术路线，该方式操作简单，能够温和地消除废催化剂的活性，同时避免了碱性废水对污水处理系统的冲击，整体工艺操作的稳定性和安全性好，废催化剂中的金属及油类资源得到有效地回收和利用，中间产物也得到循环利用，工艺成本相对较低，有利于推动离子液体烷基化工艺的绿色升级。
本发明还提供一种用于实施上述方法的系统，包括水解反应器、中和反应器、絮凝沉淀系统、机械脱水装置和干化装置；
所述水解反应器用于将氯铝酸类离子液体废催化剂与浓盐水混合进行水解反应；
所述中和反应器与所述水解反应器连接，用于将所述水解反应生成的酸性水解液与包含碱性废水的碱液混合进行中和反应；
所述絮凝沉淀系统与所述中和反应器连接，用于将所述中和反应生成的中和液与絮凝剂充分混合并实施沉降分离；
所述机械脱水装置与所述絮凝沉淀系统连接，用于对经所述沉降分离形成的浓缩絮体进行脱水处理；
所述干化装置与所述机械脱水装置连接，用于对经所述脱水处理形成的湿固渣进行干燥处理。
进一步地，所述水解反应器为平推流填充床反应器，在所述平推流填充床反应器中填充有规整填料，所述规整填料的孔隙度为0.95-0.97m 3/m 3，比表面积为300-500m 2/m 3。
本发明对水解反应器的具体结构不作严格限制，可以采用本领域公知和常用的水解反应装置。在本发明的具体方案中，采用的水解反应器包括壳体，在所述壳体的上部从上至下依次设有环形收油槽、用于分布浓盐水的布水器和用于分布氯铝酸类离子液体废催化剂的布料器，在所述壳体的下部设有用 于支承填料的填料承托架，在所述壳体的顶部设有排气口，在所述壳体的侧壁设有排油口、进水口和进料口，所述排油口与所述环形收油槽连通，所述进水口与所述布水器连通，所述进料口与所述布料器连通，在所述壳体的底部设有出液口。
鉴于废催化剂的酸性极强，而且黏度高达600-800mPa·s，并且有含有少量的机械杂质，为防止堵塞与腐蚀，优选采用氟塑料材质的机械隔膜泵对其进行输送；此外，浓盐水中的氯化钠含量高达15-22wt％，腐蚀性强，优选采用不锈钢材质的离心泵对其进行输送。
在上述水解反应器中，废催化剂与浓盐水混合进行水解反应，废催化剂中的酸溶性烃与活性组分分离，形成的酸溶油上浮至液面，经环形收油槽收集后，再经排油口及其管路自流进污油储罐以备回炼。特别是，在上述水解反应器中，将进水口及布水器分别设置在进料口及布料器的上方，不仅有利于浓盐水对废催化剂的分散，而且能够使废催化剂发生水解反应的区域远离酸溶油层，避免了水解局部放热对酸溶油品质和回收率的影响。
此外，废催化剂中含有的活性组分和酸溶性烃在水解过程中会产生挥发性有机污染物(VOCs)和氯化氢，其在水解反应器的顶部富集，为了避免对空气造成污染，可以在水解反应器的顶部设置排气口，并将气体引至浓盐水储罐的水封口，浓盐水储罐中的浓盐水既可以吸收这些气态污染物，同时也可以利用液位进行水封；水封还能为水解反应器提供正压，促进了酸性水解液对这些污染物的再吸收。
在本发明中，对水解反应器的布水器的结构不作严格限制，只要其能够使浓盐水均匀分布于水解反应器即可。
在本发明的具体方案中，所述布水器包括布水总管，在所述布水总管的两侧分别设有多个平行且等间距设置的布水支管，在每一布水支管的底部分布有多个布水孔，布水孔的总开孔面积占所述水解反应器截面积的1％以上。此时，布水器为鱼刺型；其中，相邻布水支管之间的间距可以设置为5cm以上，从而避免影响酸溶油的上浮和汇集；此外，对布水支管上的布水孔的设置方式不作严格限制，多个布水孔可以等间距设置，并且可以将多个布水孔的孔径设置为相同。
具有上述结构的布水器开孔面积大、开孔数量多，从而便于促进浓盐水 的均匀分布；此外，由于布水孔的出孔流速小、返混低，在水解反应器内形成层流流动，减弱了与废催化剂之间的传质，并且对水解液面上的酸溶油层扰动较小，更有利于酸溶油的回收。
在本发明中，对水解反应器的布料器的结构不作严格限制，只要其能够使废催化剂均匀分布于水解反应器即可。
在本发明的具体方案中，所述布料器包括布料总管，在所述布料总管的两侧分别设有多个同心且等间距设置的半圆形布料支管，在每一半圆形布料支管的底部分布有多个布料孔，布料孔的总开孔面积占所述水解反应器截面积的2％以上。此时，布料器为环型；其中，相邻布料支管之间的间距可以设置为5cm以上，从而避免影响酸溶油的上浮和汇集；此外，对布料支管上的布料孔的设置方式不作严格限制，多个布料孔可以等间距设置，并且可以将多个布料孔的孔径设置为相同，布料孔的内径例如可以设置为3-5mm。
具有上述结构的布料器开孔面积大、布料孔数量多，从而便于废催化剂布料均匀；此外，由于布料口的内径小，废催化剂以小液滴被挤出，更有利于其在浓盐水中的分散。
在本发明中，中和反应器用于将所述水解反应生成的酸性水解液与包含碱性废水的碱液混合进行中和反应；对中和反应器的具体结构不作严格限制，可以采用本领域常规的中和反应器。
在本发明的具体方案中，所述中和反应器为全混流反应器；所述中和反应器包括壳体，在所述壳体的上部从上至下依次设有用于分布碱液的布水器和用于分布中和液的布料器，在所述壳体的中部设有侧进式搅拌器，在所述壳体的顶部设有排气口，在所述壳体的侧壁设有进碱口和进液口，所述进碱口与所述布水器连通，所述进液口与所述布料器连通，在所述壳体的底部设有出液口。
本发明人的研究表明，将中和反应器的进碱口及布水器分别设置在进液口及布料器的上方，能够使中和反应生成的金属氢氧化物絮体的位置较低，从而不易堵塞布水器。特别是，采用侧进式搅拌器，加速了酸性水解液与碱液之间的传质与中和反应，同时也能防止絮体过早沉淀从而堵塞出液口及其管路。
优选地，可以采用氟塑料材质的离心泵对高含氯的酸性水解液进行 输送；碱洗废水和外源碱液高含氯、高含碱，而且需要与酸性水解液精确配比以达到中和，因此优选采用氟塑料材质的计量泵对碱洗废水和外源碱液进行输送。此外，由于酸性水解液和碱洗废水中均携带少量油分，中和过程会造成VOCs在中和反应器顶部的富集；为防止空气污染，可以在中和反应器的顶部设置排气口，并将气体引至浓盐水储罐的水封口，浓盐水储罐内的浓盐水既可以吸收这些气态污染物，也可以利用液位进行水封；水封还可为中和反应器提供正压，从而促进了中和液对这些污染物的再吸收。
对中和反应器的布水器和布料器的结构不作严格限制，其只要能够使碱液和酸性水解液均匀分布于中和反应器即可，可以采用与水解反应器中相同的结构；此时，布水器中布水孔的总开孔面积占中和反应器截面积的1％以上，布料器中布料孔的总开孔面积占中和反应器截面积的2％以上。碱洗废水与外源碱液合并后经由上述鱼刺型的布水器在中和反应器内配水，由于布水器的开孔面积大、开孔数量多，促进了碱洗废水和外源碱液在中和反应器内的均匀分布；此外，酸性水解液经由上述环型的布料器在中和反应器内配液，该布料器的开孔面积小、布料口的数量少、内径小，出液后形成局部湍流，有助于酸性水解液与碱液之间的传质和中和反应。
在本发明中，絮凝沉淀系统用于将所述中和反应生成的中和液与絮凝剂充分混合并实施沉降分离；对絮凝沉淀系统的具体结构不作严格限制，可以采用本领域常规的结构。
在本发明的具体方案中，所述絮凝沉淀系统包括依次设置的管道混合器和絮凝沉淀装置，所述絮凝沉淀装置包括密封壳体，在所述密封壳体内部设有环形溢流堰、中心管和布料管，所述布料管设置在所述中心管的内部，在所述中心管的底部设有伞型挡板，在所述密封壳体的顶部设有排气口，在所述密封壳体的侧壁设有出水口和进料口，所述出水口与所述环形溢流堰连通，所述进料口与所述布料管连通，在所述密封壳体的底部设有出渣口。
可以理解的是，中和反应器的出液口经管路与管道混合器的进口连接，在中和反应器出液口与管道混合器进口的连接管路上设有加剂口，絮凝剂配 制罐的出剂口经不锈钢材质的计量泵及管路与加剂口连接。在本发明中，管道混合器便于实现中和液与絮凝剂之间的充分接触；此外，采用不锈钢材质的计量泵进行加剂，便于使絮凝剂与中和液精确配比以达到最优的絮凝效果。
在本发明中，具有上述结构的絮凝沉淀装置为密封的竖流式沉淀池形式；含有絮体的中和液与絮凝剂经管道混合器充分混合，经自流进入上述絮凝沉淀装置进行沉淀分离，浓缩絮体的含水率降低，减轻了后续机械脱水装置的处理负荷，同时沉淀析出的浓盐水可回用于水解反应器。由于絮凝沉淀装置内的物料有可能逸出气态污染物，因此采用密封形式，同时在其顶部设置排气口将气体引至浓盐水储罐进行水封。特别是，基于分离设备的成熟度和操作上的简便性，采用上述竖流式沉淀池形式的絮凝沉淀装置进行浓盐水与絮体的分离；中和液与絮凝剂混合后经进料口进入絮凝沉淀装置，布料管将中和液向下打入中心管，经伞型挡板折流，金属氢氧化物絮体向絮凝沉淀装置的底部沉淀浓缩；同时，浓盐水向絮凝沉淀装置的顶部提升，并经环形溢流堰及出水口自流进入浓盐水储罐。当达到一定的沉淀时间，浓缩絮体与浓盐水之间的界面清晰，浓盐水几乎无絮体夹带。
采用机械脱水装置对浓缩絮体进行脱水处理可以显著降低固渣量。鉴于浓缩絮体的固含量约为2-3wt％，并且含有浓盐水，因此可以选用不锈钢材质的螺杆泵进行输送。此外，浓缩絮体中的水分以自由水为主，因此采用常规的板框压滤机或离心脱水机均可获得良好的脱水效果。鉴于板框压滤机具有占地大、处理时间长、不能连续操作等缺点，因此机械脱水装置优选为离心脱水机，其分离因数可以为3000左右，此时即能将浓缩絮体制备成含水率为60-70％的湿固渣。
由于对湿固渣进行干燥处理能够继续降低固渣产量，且更有利于回用，因此本发明的系统设置干化装置以便对经所述机械脱水装置形成的湿固渣进行干燥处理。在本发明中，可以采用螺旋输送机对湿固渣进行输送；该输送方式比较清洁，避免了带式传输的掉渣等现象。
进一步地，所述干化装置可以采用薄层干化机或低温除湿干化机，其能将湿固渣干燥为含水率10-20％的干固渣。由于干固渣中的水分主要是结晶水，继续降低含水率不仅效率低且不经济。
此外，湿固渣中的水分在除湿干燥过程中会转化为水蒸汽，回收水蒸汽 潜热并回用到干燥过程更有利于降低能耗。因此，本发明的系统还可以包括热量回收装置(即凝结水储罐)，其用于回收上述干化装置产生的凝结水；由于回收得到的凝结水的污染负荷低，因此可以回用于外源碱液及絮凝剂的配制。
可以理解的是，本发明的系统除了包括上述主体部件之外，还可以包括其它配套部件，例如废催化剂储罐、浓盐水储罐、碱洗废水储罐、外源碱液配制罐、絮凝剂配制罐、凝结水储罐、污油储罐以及各种用于输送物料的泵及输送机等，其均可以采用本领域的常规装置或部件，并且可以常规方式进行设置。
在本发明中，废催化剂储罐包括罐体，在罐体内部设有侧进式搅拌器，在罐体侧壁下端设有进料口和出料口，在罐体底部设有排空口，在罐体顶部设有气体进口；其中，侧进式搅拌器用于对来自不同时段的废催化剂进行均质均量，气体进口用于对废催化剂储罐的罐顶充氮气进行保护，以避免废催化剂与空气中的水分接触，防止水解发生爆炸。
在本发明中，浓盐水储罐包括罐体和水封管，在罐体侧壁上端设有进水口，在罐体侧壁下端设有出水口，在罐体底部设有排空口，在罐体顶部设有水封口，水封管与水封口连接。设置浓盐水储罐既为中间产物浓盐水的储存提供了空间，又为水解反应提供了原料，是整个系统中间产物循环利用的关键节点；同时，通过水封还能够控制水解反应器、中和反应器以及絮凝沉淀装置中气态污染物的逸出，避免了空气污染。
在本发明中，碱洗废水储罐包括罐体，在罐体内部设有侧进式搅拌器，在罐体侧壁下端设有进水口与出水口，在罐体底部设有排空口；其中，侧进式搅拌器用于对来自不同时段的碱洗废水进行均质均量。
在本发明中，凝结水储罐包括罐体，在罐体侧壁上端设有进水口，在罐体侧壁下端设有凝结水出口，在罐体底部设有排空口。设置凝结水储罐既为中间产物凝结水的储存提供空间，又为外源碱液和絮凝剂的配制提供了水源，是整个系统中间产物循环利用的重要节点。
进一步地，本发明的系统包括机械隔膜泵和离心泵，所述废催化剂储罐通过所述机械隔膜泵与所述水解反应器的进料口连接，所述浓盐水储罐通过所述离心泵与所述水解反应器的进水口连接，所述水解反应器的排油口与污 油储罐连接。
进一步地，本发明的系统包括离心泵和计量泵，所述水解反应器的出液口通过所述离心泵与所述中和反应器的进液口连接，所述碱洗废水储罐和外源碱液配制罐分别通过所述计量泵与所述中和反应器的进碱口连接，所述中和反应器的出液口与所述管道混合器连接。
进一步地，本发明的系统包括计量泵，所述凝结水储罐分别通过所述计量泵与外源碱液配制罐的进水口及絮凝剂配制罐的进水口连接。采用计量泵输送凝结水，便于对外源碱液和絮凝剂的浓度进行精确控制。
特别是，所述水解反应器的排气口、所述中和反应器的排气口、所述絮凝沉淀系统的出水口和排气口分别通过管路与浓盐水储罐的水封口连接。
此外，所述絮凝沉淀系统和机械脱水装置具有浓盐水出口，所述浓盐水出口与所述浓盐水储罐连接，从而便于对浓盐水进行回用。
本发明的系统是针对氯铝酸类离子液体废催化剂和与碱洗废水的特性而提出的，其利用水解反应器和中和反应器实现了废催化剂和碱洗废水的无害化和油类资源回收，并且利用絮凝沉淀系统、机械脱水装置和干化装置实现了金属固渣的减量化和资源化；此外，利用浓盐水储罐和凝结水储罐实现了中间产物的循环利用。整个系统的运行过程温和，操作过程安全，无新增污染源，对资源的回收率高，特别是回收得到的酸溶油中水及杂质的含量低，油品的品质高。
附图说明
图1为本发明一实施方式的对氯铝酸类离子液体废催化剂和碱性废水进行处理的工艺流程图；
图2为本发明一实施方式的处理氯铝酸类离子液体废催化剂和碱性废水的系统的结构示意图；
图3为本发明一实施方式的水解反应器的结构示意图；
图4为图3的A-A截面示意图；
图5为本发明一实施方式的水解反应器的环形收油槽的结构示意图；
图6为本发明一实施方式的布水器的结构示意图；
图7为本发明一实施方式的布料器的结构示意图；
图8为图7的B-B截面示意图；
图9为本发明一实施方式的中和反应器的结构示意图；
图10为本发明一实施方式的絮凝沉淀装置的结构示意图。
附图标记说明：
1：水解反应器；11：壳体；12：环形收油槽；13：布水器；14：布料器；15：填料承托架；16：排气口；17：排油口；18：进水口；19：进料口；110：出液口；111：溢流堰；112：填料层；
2：中和反应器；21：壳体；22：布水器；23：布料器；24：侧进式搅拌器；25：排气口；26：进碱口；27：进液口；28：出液口；
3：絮凝沉淀装置；31：密封壳体；32：环形溢流堰；33：中心管；34：布料管；35：伞型挡板；36：排气口；37：出水口；38：进料口；39：出渣口；
4：机械脱水装置；5：干化装置；
61：废催化剂储罐；611：气体进口；62：浓盐水储罐；63：碱洗废水储罐；64：外源碱液配制罐；65：絮凝剂配制罐；66：凝结水储罐；67：污油储罐；
71：机械隔膜泵；72、77：离心泵；73、74、75、76：计量泵；78：螺杆泵；
8：管道混合器；9：螺旋输送机；10：料仓；
101：布水总管；102：布水支管；
201：布料总管；202：布料支管；203：布料孔。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合本发明的实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
各实施例的原料如下：
氯铝酸类离子液体废催化剂：为利用氯铝酸类离子液体催化碳四生产烷基化油产生的废催化剂，黏度约为740mPa·s，活性组分主要为氯化铝和氯化铜，总含量约占85wt％；其他组分为酸溶性烃，含量约占15wt％。
碱性废水：为利用氯铝酸类离子液体催化碳四生产烷基化油产生的碱洗废水，氢氧化钠浓度约为12wt％。
对上述氯铝酸类离子液体废催化剂和碱性废水进行处理的方法，具体包括：首先，将氯铝酸类离子液体废催化剂与浓盐水混合进行水解反应，直至完全消除废催化剂的残留活性，生成酸性水解液和酸溶油，酸溶油经沉降与酸性水解液分离至上层被回收；随后，将酸性水解液、碱洗废水以及配制的外源碱液混合进行中和反应，直至体系为弱碱性，生成含有金属氢氧化物絮体的中和液；将中和液与絮凝剂充分混合后进行沉降分离，底部生成浓缩絮体，上层析出的浓盐水回用于与废催化剂的水解反应；对上述浓缩絮体进行机械脱水处理，生成含水率约60-70wt％的湿固渣，从浓缩絮体中分离出的浓盐水回用于废催化剂的水解反应；对上述湿固渣进行干燥处理，生成含水率约10-20wt％的干化固渣，干燥过程产生的水蒸汽经凝结后回用于外源碱液与絮凝剂溶液的配制。
实施例1
以产量为30万吨/年的氯铝酸类复合离子液体烷基化装置为例，该装置在生产过程排放废催化剂的量为2140吨/年，废催化剂汇集于废催化剂储罐储存待用；同时，该装置在生产过程排放碱洗废水的量为6340吨/年。
如图1所示，本实施例处理氯铝酸类离子液体废催化剂和碱性废水的方法，步骤如下：
1、配制试剂
在浓盐水储罐中配制浓度为15wt％左右的氯化钠溶液(即浓盐水)，储存备用。
在碱液配制罐中配制浓度为30wt％左右的氢氧化钠溶液(即外源碱液)，储存备用。
在絮凝剂配制罐中配制浓度为0.5wt％左右的絮凝剂溶液，储存备用；其中， 絮凝剂为阴离子聚丙烯酰胺，其相对分子量为1500万，电荷密度为20％。
上述试剂在开工前均采用新鲜水(例如自来水)进行配制；在运行后，碱液和絮凝剂的配制采用来自干化装置的凝结水，浓盐水的配制采用来自絮凝沉淀装置和机械脱水装置的浓盐水。
2、水解反应
255kg/h的废催化剂经氟塑料机械隔膜泵提升，12457kg/h的浓盐水经不锈钢离心泵提升，废催化剂与浓盐水与按1：50的进料体积比，分别进入水解反应器进行水解反应。水解反应在平推流填充床反应器中进行，在平推流填充床反应器中填充有规整填料，废催化剂与浓盐水以平推流的流态在填料层进行水解反应；其中，规整填料选用聚氯乙烯材质的Y型波纹孔板规整填料，其比表面积为350m 2/m 3，孔隙度为0.95m 3/m 3，水解反应器填料层的空速控制在0.25h -1。待水解反应产物的pH值稳定在2.6左右，废催化剂的残留活性被完全消除。
对水解反应产物进行沉降分离，分别得到酸性水解液和酸溶油；其中，酸性水解液的pH值为2.6左右，含油量约为120mg/L；同时，40kg/h左右的酸溶油通过自流回收进入污油储罐中进行储存。酸溶油的构成为环戊二烯类化合物，其可以定期送往延迟焦化装置作为原料再利用。
3、中和反应
12672kg/h的酸性水解液经氟塑料离心泵提升，754kg/h碱洗废水和251kg/h外源碱液经氟塑料计量泵提升，酸性水解液、碱洗废水和外源碱液按50：3：1的进料体积比分别进入中和反应器中进行中和反应。中和反应在全混流反应器中进行，酸性水解液、碱洗废水和外源碱液以全混流的流态进行快速的中和反应；其中，中和反应器的空速控制在1h -1，中和液的pH值达到8.5左右时，酸性水解液完全中和，此时中和液的含油量约为120mg/L，氯化钠含量约为20wt％，氢氧化铝/氢氧化铜絮体的含量约为2.8wt％。
4、絮凝
向中和液中加入0.5wt％的絮凝剂溶液，控制中和液与絮凝剂溶液的质量比为230：1(即絮凝剂投加量为每吨中和液加入絮凝剂22g左右)，在管道混合器内充分混合后，自流进入絮凝沉淀装置中进行沉降分离。
在实施沉降分离2小时后，浓缩絮体层体积占絮凝沉淀装置内物料体积的 25％左右，浓缩絮体的浓盐水含量约为90wt％。絮凝沉淀装置内物料体积的75wt％为浓盐水，石油类含量约为150mg/L，浓盐水自流进浓盐水储罐，回用于水解反应器。
5、脱水处理
浓缩絮体经不锈钢螺杆泵输送进入离心脱水机(即机械脱水装置)进行脱水处理，其中离心脱水机的分离因数为3000左右；脱水生成的含水率为70wt％左右的湿固渣自卸进入料仓，从浓缩絮体中分离出的浓盐水含油量为100mg/L，浓盐水自流进浓盐水储罐，回用于水解反应器。
6、干燥处理
料仓中的湿固渣经不锈钢螺旋输送机送入薄层干化机(即干化装置)，生成454kg/h的含水率为15wt％的干固渣。该干固渣中氯化钠的含量约为54.7wt％，氢氧化铝的含量约为22.5wt％，氢氧化铜的含量约为6.7wt％，含油量小于1wt％，可以作为一般固废出厂或者作为冶金原料利用。
薄层干化机干化过程产生的凝结水CODcr约为500mg/L，几乎不含油和盐类，自流进入凝结水储罐，回用于碱液与絮凝剂溶液的配制。
上述处理过程的实施，也可同时参考图2示出的处理系统示意图。
经上述处理后，废催化剂中酸溶油的回收率达到90％左右；此外，经检测，回收得到的酸溶油的含水率为1wt％左右，且未检测到碳颗粒杂质，回收油品的品质高。
实施例2
本实施例处理氯铝酸类离子液体废催化剂和碱性废水的方法，步骤如下：
1、配制试剂
在浓盐水储罐中配制浓度为22wt％左右的氯化钠溶液(即浓盐水)，储存备用。
在碱液配制罐中配制浓度为30wt％左右的氢氧化钠溶液(即外源碱液)，储存备用。
在絮凝剂配制罐中配制浓度为0.5wt％左右的絮凝剂溶液，储存备用；其中，絮凝剂为阴离子聚丙烯酰胺，其相对分子量为1800万，电荷密度为10％。
上述试剂在开工前均采用新鲜水(例如自来水)进行配制；在运行后，碱液和絮凝剂的配制采用来自干化装置的凝结水，浓盐水的配制采用来自絮凝沉淀装置和机械脱水装置的浓盐水。处理工序以及使用的系统依然可参考图1和图2。
2、水解反应
废催化剂经氟塑料机械隔膜泵提升，浓盐水经不锈钢离心泵提升，废催化剂与浓盐水与按1：60的进料体积比，分别进入水解反应器进行水解反应。水解反应在平推流填充床反应器中进行，在平推流填充床反应器中填充有规整填料，废催化剂与浓盐水以平推流的流态在填料层进行水解反应；其中，规整填料选用聚氯乙烯材质的Y型波纹孔板规整填料，其比表面积为500m 2/m 3，孔隙度为0.97m 3/m 3，水解反应器填料层的空速控制在0.5h -1。待水解反应产物的pH值稳定在2.6左右，废催化剂的残留活性被完全消除。
对水解反应产物进行沉降分离，分别得到酸性水解液和酸溶油；其中，酸性水解液的pH值为2.6左右，含油量约为120mg/L；同时，酸溶油通过自流回收进入污油储罐中进行储存。酸溶油的构成为环戊二烯类化合物，其可以定期送往延迟焦化装置作为原料再利用。
3、中和反应
酸性水解液经氟塑料离心泵提升，碱洗废水和外源碱液经氟塑料计量泵提升，酸性水解液、碱洗废水和外源碱液按一定的进料体积比分别进入中和反应器中进行中和反应，使中和液中氯化钠的浓度为30wt％左右。中和反应在全混流反应器中进行，酸性水解液、碱洗废水和外源碱液以全混流的流态进行快速的中和反应；其中，中和反应器的空速控制在2h -1，中和液的pH值达到8.5左右时，酸性水解液完全中和，此时中和液的含油量约为60mg/L，氯化钠含量约为23wt％，氢氧化铝/氢氧化铜絮体的含量约为2.8wt％。
4、絮凝
向中和液中加入0.5wt％的絮凝剂溶液，控制絮凝剂投加量为每吨中和液加入絮凝剂30g左右，在管道混合器内充分混合后，自流进入絮凝沉淀装置中进行沉降分离。
在实施沉降分离3小时左右后，浓缩絮体层体积占絮凝沉淀装置内物料体积的20％左右，浓缩絮体的浓盐水含量约为85wt％。絮凝沉淀装置内物料体积 的97wt％为浓盐水，石油类含量约为50mg/L，浓盐水自流进浓盐水储罐，回用于水解反应器。
5、脱水处理
浓缩絮体经不锈钢螺杆泵输送进入离心脱水机(即机械脱水装置)进行脱水处理，其中离心脱水机的分离因数为3000左右；脱水生成的含水率为70wt％左右的湿固渣自卸进入料仓，从浓缩絮体中分离出的浓盐水含油量为50mg/L，浓盐水自流进浓盐水储罐，回用于水解反应器。
6、干燥处理
料仓中的湿固渣经不锈钢螺旋输送机送入薄层干化机(即干化装置)，生成含水率为15wt％左右的干固渣。该干固渣中氯化钠的含量约为55wt％，氢氧化铝的含量约为22wt％，氢氧化铜的含量约为7wt％，含油量小于1wt％，可以作为一般固废出厂或者作为冶金原料利用。
薄层干化机干化过程产生的凝结水CODcr约为500mg/L，几乎不含油和盐类，自流进入凝结水储罐，回用于碱液与絮凝剂溶液的配制。
经上述处理后，废催化剂中酸溶油的回收率达到90％左右；此外，经检测，回收得到的酸溶油的含水率为1wt％左右，且未检测到碳颗粒杂质，回收油品的品质高。
实施例3
结合图2至图10所示，本发明的处理氯铝酸类离子液体废催化剂和碱性废水的系统，包括水解反应器1、中和反应器2、絮凝沉淀系统、机械脱水装置4和干化装置5；水解反应器1用于将氯铝酸类离子液体废催化剂与浓盐水混合进行水解反应；中和反应器2与水解反应器1连接，用于将水解反应生成的酸性水解液与包含碱性废水的碱液混合进行中和反应；絮凝沉淀系统与中和反应器2连接，用于将中和反应生成的中和液与絮凝剂充分混合并实施沉降分离；机械脱水装置4与絮凝沉淀系统连接，用于对经沉降分离形成的浓缩絮体进行脱水处理；干化装置5与机械脱水装置4连接，用于对经脱水处理形成的湿固渣进行干燥处理。
本发明的系统通过分别设置水解反应器1和中和反应器2，从而在采用碱液对废催化剂进行中和反应之前，先将氯铝酸类离子液体废催化剂 与浓盐水在水解反应器1中混合进行水解反应；在水解反应器1中，大量的浓盐水在废催化剂的水解过程中能够将水解反应产生的热快速分散，从而将水解反应的自加速机制打断；同时，浓盐水中高浓度的氯离子增加了水解产物的浓度，对水解反应具有一定的抑制作用。上述方式不仅能够温和地消除废催化剂的活性，同时能够消除中和反应热对水解反应速率的促进作用，使整个系统的操作过程更加稳定和安全。
本发明的系统可用于实施例1或实施例2的方法；下面对本发明系统的各部件的结构进行详细说明。
1、水解反应器
在一实施方式中，水解反应器1设置为平推流填充床反应器，其能够使水解反应更加温和，从而实现温和水解；此时，废催化剂与浓盐水在水解反应器1中以平推流状态进行接触，物料的返混程度低，对废催化剂液滴的扰动小，活性组分与水分之间的传质被弱化，不仅降低了水解反应的强度，而且有利于酸溶油的分离与回收。
进一步地，在平推流填充床反应器中填充规整填料，该方式综合利用了废催化剂的高黏度特性、在填料表面的边界层特性以及填料对催化剂的截留作用；由于废催化剂的黏度高、进料量小，其在规整填料表面呈膜状的层流流动，并形成较厚的层流边界层，较大的黏性力使废催化剂的沉降速率被有效控制。此外，由于边界层内层流底层的存在，物料间的传质阻力增大，因此废催化剂与浓盐水之间的传质效率也被有效控制。相对于散堆填料，规整填料的物料流通孔道均匀，不易出现沟流现象。
特别是，通过采用高通量的规整填料，能为浓盐水提供通畅的流路，并基本保持层流状态，同时能减弱与废催化剂之间的传质。在进行水解反应时，废催化剂在规整填料的孔隙中均匀分布，形成数量众多的微元反应环境，大体量的浓盐水与废催化剂的接触时间长，从而保证了对废催化剂的彻底水解。具体地，规整填料的孔隙度为0.95-0.97m 3/m 3，比表面积在300-500m 2/m 3；此时，水解反应的速率控制较好，既不易造成孔道堵塞，同时水解反应易完全进行。
进一步地，规整填料可以为疏油性填料并且可以具有斜板结构；该规整填料还能够促进对酸溶油滴的粗粒化，使大颗粒油滴更容易上浮，从而有利 于酸溶油的回收。本发明对规整填料的具体结构及材质不作严格限制；规整填料例如可以为Y型波纹孔板规整填料等，其波纹与轴线的倾角可以为45°左右，从而对废催化剂液滴的截留效果好。此外，规整填料的材质可以为聚乙烯(PE)、聚氯乙烯(PVC)或聚偏氟乙烯(PVDF)，其具有疏油性且耐酸耐氯腐蚀，有利于酸溶油的粗粒化，从而便于酸溶油回收。
特别是，上述平推流填充床反应器的空速可以为0.25-0.5h -1。其中，当空速为0.5h -1时，废催化剂得以完全水解，pH值能够稳定在2.5-2.8；当空速为0.25h -1时，酸性水解液的含油量最低，回收得到的酸溶油最多。
结合图3至图5所示，水解反应器1包括壳体11，在壳体11的上部从上至下依次设有环形收油槽12、用于分布浓盐水的布水器13和用于分布氯铝酸类离子液体废催化剂的布料器14，在壳体11的下部设有用于支承填料的填料承托架15，在壳体11的顶部设有排气口16，在壳体11的侧壁设有排油口17、进水口18和进料口19，排油口17与环形收油槽12连通，进水口18与布水器13连通，进料口19与布料器14连通，在壳体11的底部设有出液口110。
可以理解的是，上述规整填料装填在填料承托架15上(参见图4)，从而形成填料层112；此外，还可以在环形收油槽12的上方设置溢流堰111，以便维持油层并使酸溶油均匀溢出。
进一步地，鉴于废催化剂的酸性极强，而且黏度高达600-800mPa·s，并且有含有少量的机械杂质，为防止堵塞与腐蚀，优选采用氟塑料材质的机械隔膜泵71对其进行输送；此外，浓盐水中的氯化钠含量高达15-22wt％，腐蚀性强，优选采用不锈钢材质的离心泵72对其进行输送。
在上述水解反应器1中，废催化剂与浓盐水混合进行水解反应，废催化剂中的酸溶性烃与活性组分分离，形成的酸溶油上浮至液面，经环形收油槽12收集后，再经排油口17及其管路自流进污油储罐67以备回炼(参见图5)。特别是，在上述水解反应器1中，将进水口18及布水器13分别设置在进料口19及布料器14的上方，不仅有利于浓盐水对废催化剂的分散，而且能够使废催化剂发生水解反应的区域远离酸溶油层，避免了水解局部放热对酸溶油品质和回收率的影响。
此外，废催化剂中含有的活性组分和酸溶性烃在水解过程中会产生挥发 性有机污染物(VOCs)和氯化氢，其在水解反应器1的顶部富集，为了避免对空气造成污染，可以在水解反应器1的顶部设置排气口16，并将气体引至浓盐水储罐62的水封口，浓盐水储罐62中的浓盐水既可以吸收这些气态污染物，同时也可以利用液位进行水封；水封还可为水解反应器1提供正压，促进了酸性水解液对这些污染物的再吸收。
在本发明中，对水解反应器1的布水器13和布料器14的结构不作严格限制，只要其能够使浓盐水和废催化剂均匀分布于水解反应器1即可。
具体地，如图6所示，在一实施方式中，布水器13包括布水总管101，在布水总管101的两侧分别设有多个平行且等间距设置的布水支管102，在每一布水支管102的底部分布有多个布水孔(未图示)，布水孔的总开孔面积占水解反应器1截面积的1％以上。此时，布水器13为鱼刺型；其中，相邻布水支管102之间的间距可以设置为5cm以上，从而避免影响酸溶油的上浮和汇集；此外，对布水支管102上的布水孔的设置方式不作严格限制，多个布水孔可以等间距设置，并且可以将多个布水孔的孔径设置为相同。
具有上述结构的布水器13的开孔面积大、开孔数量多，从而便于促进浓盐水的均匀分布；此外，由于布水孔的出孔流速小、返混低，在水解反应器1内形成层流流动，减弱了与废催化剂之间的传质，并且对水解液面上的酸溶油层扰动较小，更有利于酸溶油的回收。
如图7和图8所示，在一实施方式中，布料器14包括布料总管201，在布料总管201的两侧分别设有多个同心且等间距设置的半圆形布料支管202，在每一半圆形布料支管202的底部分布有多个布料孔203(参见图7)，布料孔203的总开孔面积占水解反应器1截面积的2％以上。此时，布料器14为环型；其中，相邻布料支管202之间的间距可以设置为5cm以上，从而避免影响酸溶油的上浮和汇集；此外，对布料支管202上的布料孔203的设置方式不作严格限制，多个布料孔203可以等间距设置，并且可以将多个布料孔203的孔径设置为相同，布料孔203的内径例如可以设置为3-5mm。
具有上述结构的布料器14的开孔面积大、布料孔数量多，从而便于废催化剂布料均匀；此外，由于布料孔203的内径小，废催化剂以小液滴被挤出，更有利于其在浓盐水中的分散。
2、中和反应器
中和反应器2用于将水解反应生成的酸性水解液与包含碱性废水的碱液混合进行中和反应；对中和反应器2的具体结构不作严格限制，可以采用本领域常规的中和反应器。
具体地，中和反应器2设置为全混流反应器；如图9所示，中和反应器2包括壳体21，在壳体21的上部从上至下依次设有用于分布碱液的布水器22和用于分布中和液的布料器23，在壳体21的中部设有侧进式搅拌器24，在壳体21的顶部设有排气口25，在壳体21的侧壁设有进碱口26和进液口27，进碱口26与布水器22连通，进液口27与布料器23连通，在壳体21的底部设有出液口28。
将中和反应器2的进碱口26及布水器22设置在进液口27及布料器23的上方，能够使中和反应生成的金属氢氧化物絮体的位置较低，从而不易堵塞布水器22。特别是，采用侧进式搅拌器24，加速了酸性水解液与碱液之间的传质与中和反应，同时也能防止絮体过早沉淀从而堵塞出液口28及其管路。
优选地，可以采用氟塑料材质的离心泵77对高含氯的酸性水解液进行输送；碱洗废水和外源碱液高含氯、高含碱，而且需要与酸性水解液精确配比以达到中和，因此优选采用氟塑料材质的计量泵73、74对碱洗废水和外源碱液进行输送。此外，由于酸性水解液和碱洗废水中均携带少量油分，中和过程会造成VOCs在中和反应器2顶部的富集；为防止空气污染，可以在中和反应器2的顶部设置排气口25，并将气体引至浓盐水储罐62的水封口，浓盐水储罐62内的浓盐水既可以吸收这些气态污染物，也可以利用液位进行水封；水封还可为中和反应器2提供正压，从而促进了中和液对这些污染物的再吸收。
对中和反应器2的布水器22和布料器23的结构不作严格限制，其只要能够使碱液和酸性水解液均匀分布于中和反应器2即可，可以采用与水解反应器1中相同的结构。碱洗废水与外源碱液合并后经由上述鱼刺型的布水器22在中和反应器2内配水，由于布水器22的开孔面积大、开孔数量多，促进了碱洗废水和外源碱液在中和反应器2内的均匀分布；此外，酸性水解液经由上述环型的布料器23在中和反应器2内配液，该布料器23的开孔面积小、布料口的数量少、内径小，出液后形成局部湍流，有 助于酸性水解液与碱液之间的传质和中和反应。
3、絮凝沉淀系统
絮凝沉淀系统用于将中和反应生成的中和液与絮凝剂充分混合并实施沉降分离；对絮凝沉淀系统的具体结构不作严格限制，可以采用本领域常规的结构。
具体地，絮凝沉淀系统包括依次设置的管道混合器8和絮凝沉淀装置3；如图10所示，絮凝沉淀装置3包括密封壳体31，在密封壳体31内部设有环形溢流堰32、中心管33和布料管34，布料管34设置在中心管33的内部，在中心管33的底部设有伞型挡板35，在密封壳体31的顶部设有排气口36，在密封壳体31的侧壁设有出水口37和进料口38，出水口37与环形溢流堰32连通，进料口38与布料管34连通，在密封壳体31的底部设有出渣口39。
可以理解的是，中和反应器2的出液口28经管路与管道混合器8的进口连接，在中和反应器2出液口28与管道混合器8进口的连接管路上设有加剂口，絮凝剂配制罐65的出剂口经不锈钢材质的计量泵75及管路与加剂口连接。在本发明中，管道混合器8便于实现中和液与絮凝剂之间的充分接触；此外，采用不锈钢材质的计量泵75进行加剂，便于使絮凝剂与中和液精确配比以达到最优的絮凝效果。
具有上述结构的絮凝沉淀装置3为密封的竖流式沉淀池形式；含有絮体的中和液与絮凝剂经管道混合器8充分混合，经自流进入上述絮凝沉淀装置3进行沉淀分离，浓缩絮体的含水率降低，减轻了后续机械脱水装置4的处理负荷，同时沉淀析出的浓盐水可回用于水解反应器1。由于絮凝沉淀装置3内的物料有可能逸出气态污染物，因此采用密封形式，同时在其顶部设置的排气口36将气体引至浓盐水储罐62进行水封。特别是，基于分离设备的成熟度和操作上的简便性，采用上述竖流式沉淀池形式的絮凝沉淀装置3进行浓盐水与絮体的分离；中和液与絮凝剂混合后经进料口38进入絮凝沉淀装置3，布料管34将中和液向下打入中心管33，经伞型挡板35折流，金属氢氧化物絮体向絮凝沉淀装置3的底部沉淀浓缩；同时，浓盐水向絮凝沉淀装置3的顶部提升，并经环形溢流堰32及出水口37自流进入浓盐水储罐62。当达到一定的沉淀时间，浓缩絮体与浓盐水之间的界面清晰，浓盐水几乎无絮 体夹带。
4、机械脱水装置
机械脱水装置4用于对浓缩絮体进行脱水处理，从而显著降低固渣量；鉴于浓缩絮体的固含量约为2-3wt％，并且含有浓盐水，因此可以选用不锈钢材质的螺杆泵78进行输送。此外，浓缩絮体中的水分以自由水为主，因此采用常规的板框压滤机或离心脱水机均可获得良好的脱水效果。鉴于板框压滤机具有占地大、处理时间长、不能连续操作等缺点，因此机械脱水装置4优选为离心脱水机，其分离因数可以为3000左右，此时即能将浓缩絮体制备成含水率为60-70％的湿固渣。
5、干化装置
干化装置5用于对经机械脱水处理形成的湿固渣进行干燥处理，从而继续降低固渣产量，并且利于回用。其中，可以采用螺旋输送机9对湿固渣进行输送；该输送方式比较清洁，避免了带式传输的掉渣等现象。
上述湿固渣中的水分主要是毛细水，无论采用板框压滤还是离心脱水方式均难以继续降低其含水率和固渣产量，利用干燥方式进行除湿干化更为适合。因此，干化装置5可以采用薄层干化机或低温除湿干化机，其能将湿固渣干燥为含水率10-20％的干固渣。
薄层干化机耦合了传导和辐射干燥原理，一般采用热流体间接加热方式，其对湿固渣中水分的汽化速度快，然而能耗和设备投资较高；低温除湿干化机是基于对流干燥原理，一般采用电直接加热方式，气化除湿的速度要比薄层干燥慢，然而设备投资低，工艺操作简单。在存在余热介质(如蒸汽)可以利用的情况下，优选采用薄层干化机。由于干固渣中的水分主要是结晶水，继续降低含水率不仅效率低且不经济。
此外，湿固渣中的水分在除湿干燥过程中会转化为水蒸汽，回收水蒸汽潜热并回用到干燥过程更有利于降低能耗。因此，本发明的系统还可以包括热量回收装置(即凝结水储罐6666)，其用于回收上述干化装置5产生的凝结水；由于回收得到的凝结水的污染负荷低，因此可以回用于外源碱液及絮凝剂的配制。
6、其它配套部件
可以理解的是，本发明的系统除了包括上述主体部件之外，还包括 其它配套部件，其中包括废催化剂储罐61、浓盐水储罐62、碱洗废水储罐63、外源碱液配制罐64、絮凝剂配制罐65、凝结水储罐66、污油储罐67以及上述提及的各种用于输送物料的泵及输送机等，其均可以采用本领域的常规装置或部件，并且可以常规方式进行设置。
具体地，废催化剂储罐61包括罐体，在罐体内部设有侧进式搅拌器，在罐体侧壁下端设有进料口和出料口，在罐体底部设有排空口，在罐体顶部设有气体进口611；其中，侧进式搅拌器用于对来自不同时段的废催化剂进行均质均量，气体进口611用于对废催化剂储罐61的罐顶充氮气进行保护，以避免废催化剂与空气中的水分接触，防止水解发生爆炸。
浓盐水储罐62包括罐体和水封管，在罐体侧壁上端设有进水口，在罐体侧壁下端设有出水口，在罐体底部设有排空口，在罐体顶部设有水封口，水封管与水封口连接。设置浓盐水储罐62既为中间产物浓盐水的储存提供了空间，又为水解反应提供了原料，是整个系统中间产物循环利用的关键节点；同时，通过水封还能够控制水解反应器、中和反应器以及絮凝沉淀装置中气态污染物的逸出，避免了空气污染。
碱洗废水储罐63包括罐体，在罐体内部设有侧进式搅拌器，在罐体侧壁下端设有进水口与出水口，在罐体底部设有排空口；其中，侧进式搅拌器用于对来自不同时段的碱洗废水进行均质均量。
凝结水储罐66包括罐体，在罐体侧壁上端设有进水口，在罐体侧壁下端设有凝结水出口，在罐体底部设有排空口。设置凝结水储罐66既为中间产物凝结水的储存提供空间，又为外源碱液和絮凝剂的配制提供了水源，是整个系统中间产物循环利用的重要节点。
进一步地，废催化剂储罐61通过机械隔膜泵71与水解反应器1的进料口19连接，浓盐水储罐62通过离心泵72与水解反应器1的进水口18连接，水解反应器1的排油口17与污油储罐67连接。
进一步地，水解反应器1的出液口110通过离心泵77与中和反应器2的进液口27连接，碱洗废水储罐63和外源碱液配制罐64分别通过计量泵73、74与中和反应器2的进碱口26连接，中和反应器2的出液口28与管道混合器8的进口连接。
进一步地，管道混合器8的出口与絮凝沉淀装置3的进料口38连接，絮 凝沉淀装置3的出渣口39通过螺杆泵78与机械脱水装置4的进口连接。
进一步地，机械脱水装置4的排渣口与料仓10连接；料仓10通过螺旋输送机9与干化装置5的进口连接；此外，凝结水储罐66与干化装置5连接以回收凝结水。凝结水储罐66还通过计量泵76与外源碱液配制罐64的进水口及絮凝剂配制罐65的进水口连接。
特别是，水解反应器1的排气口16、中和反应器2的排气口25、絮凝沉淀装置的出水口37和排气口36分别通过管路与浓盐水储罐62的水封口连接。
此外，絮凝沉淀装置3和机械脱水装置4具有浓盐水出口，浓盐水出口与浓盐水储罐62连接，从而便于对浓盐水进行回用。
本发明的系统利用水解反应器1和中和反应器2实现了废催化剂和碱洗废水的无害化和油类资源回收，并且利用絮凝沉淀系统、机械脱水装置4和干化装置5实现了金属固渣的减量化和资源化；此外，利用浓盐水储罐62和凝结水储罐66实现了中间产物的循环利用。整个系统的运行过程温和，操作过程安全，无新增污染源，对资源的回收率高，特别是回收得到的酸溶油中水及杂质的含量低，油品的品质高。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (20)

  1. 一种处理氯铝酸类离子液体废催化剂和碱性废水的方法，其特征在于，包括如下步骤：
    1)将氯铝酸类离子液体废催化剂与浓盐水混合进行水解反应，至氯铝酸类离子液体废催化剂的残留活性完全消除，对水解反应产物进行分离，分别得到酸性水解液和酸溶油；
    2)将所述酸性水解液与包含碱性废水的碱液混合进行中和反应，至反应体系为弱碱性，得到含有金属氢氧化物絮体的中和液；
    3)将所述中和液与絮凝剂充分混合并实施沉降分离，收取上层的浓盐水回用于所述水解反应，同时收取下层的浓缩絮体；
    4)对所述浓缩絮体进行脱水处理，收取湿固渣，并将脱出的浓盐水回用于所述水解反应；
    5)对所述湿固渣进行干燥处理，得到干化固渣。
  2. 根据权利要求1所述的方法，其特征在于，步骤1)中，所述浓盐水中氯化钠的含量为15-22wt％，所述氯铝酸类离子液体废催化剂与浓盐水的进料体积比为1：(50-60)。
  3. 根据权利要求1或2所述的方法，其特征在于，步骤1)中，所述水解反应在平推流填充床反应器中进行，在所述平推流填充床反应器中填充有规整填料。
  4. 根据权利要求3所述的方法，其特征在于，所述规整填料的孔隙度为0.95-0.97m 3/m 3，比表面积为300-500m 2/m 3。
  5. 根据权利要求3所述的方法，其特征在于，所述平推流填充床反应器的空速为0.25-0.5h -1。
  6. 根据权利要求3或4所述的方法，其特征在于，所述规整填料为Y型波纹孔板规整填料；所述规整填料的材质为聚乙烯、聚氯乙烯或聚偏氟乙烯。
  7. 根据权利要求1或2所述的方法，其特征在于，氯铝酸类离子液体废催化剂与浓盐水混合进行水解反应，酸性水解液的pH基本稳定在2.5-2.8，所述水解反应完成。
  8. 根据权利要求1所述的方法，其特征在于，步骤2)中，所述中和反 应在全混流反应器中进行，所述全混流反应器的空速为1-2h -1。
  9. 根据权利要求1或8所述的方法，其特征在于，步骤2)中，所述中和液的pH值为8.0-8.5。
  10. 根据权利要求1所述的方法，其特征在于，步骤3)中，所述絮凝剂为阴离子型聚丙烯酰胺，所述阴离子型聚丙烯酰胺的相对分子量为600-1800万，电荷密度为10-40％。
  11. 根据权利要求10所述的方法，其特征在于，所述絮凝剂的投加量为每吨中和液加入絮凝剂20-30g，所述沉降分离的时间为2-3小时。
  12. 根据权利要求1所述的方法，其特征在于，所述氯铝酸类离子液体废催化剂为利用氯铝酸类离子液体催化碳四生产烷基化油产生的废催化剂；所述碱性废水为利用氯铝酸类离子液体催化碳四生产烷基化油产生的碱洗废水。
  13. 一种用于实施权利要求1至12任一所述方法的系统，其特征在于，包括水解反应器、中和反应器、絮凝沉淀系统、机械脱水装置和干化装置；
    所述水解反应器用于将氯铝酸类离子液体废催化剂与浓盐水混合进行水解反应；
    所述中和反应器与所述水解反应器连接，用于将所述水解反应生成的酸性水解液与包含碱性废水的碱液混合进行中和反应；
    所述絮凝沉淀系统与所述中和反应器连接，用于将所述中和反应生成的中和液与絮凝剂充分混合并实施沉降分离；
    所述机械脱水装置与所述絮凝沉淀系统连接，用于对经所述沉降分离形成的浓缩絮体进行脱水处理；
    所述干化装置与所述机械脱水装置连接，用于对经所述脱水处理形成的湿固渣进行干燥处理。
  14. 根据权利要求13所述的系统，其特征在于，所述水解反应器包括壳体，在所述壳体的上部从上至下依次设有环形收油槽、用于分布浓盐水的布水器和用于分布氯铝酸类离子液体废催化剂的布料器，在所述壳体的下部设有用于支承填料的填料承托架，在所述壳体的顶部设有排气口，在所述壳体的侧壁设有排油口、进水口和进料口，所述排油口与 所述环形收油槽连通，所述进水口与所述布水器连通，所述进料口与所述布料器连通，在所述壳体的底部设有出液口。
  15. 根据权利要求13所述的系统，其特征在于，所述中和反应器为全混流反应器；所述中和反应器包括壳体，在所述壳体的上部从上至下依次设有用于分布碱液的布水器和用于分布中和液的布料器，在所述壳体的中部设有侧进式搅拌器，在所述壳体的顶部设有排气口，在所述壳体的侧壁设有进碱口和进液口，所述进碱口与所述布水器连通，所述进液口与所述布料器连通，在所述壳体的底部设有出液口。
  16. 根据权利要求14或15所述的系统，其特征在于，所述布水器包括布水总管，在所述布水总管的两侧分别设有多个平行且等间距设置的布水支管，在每一布水支管的底部分布有多个布水孔，布水孔的总开孔面积占反应器截面积的1％以上。
  17. 根据权利要求14或15所述的系统，其特征在于，所述布料器包括布料总管，在所述布料总管的两侧分别设有多个同心且等间距设置的半圆形布料支管，在每一半圆形布料支管的底部分布有多个布料孔，布料孔的总开孔面积占反应器截面积的2％以上。
  18. 根据权利要求13所述的系统，其特征在于，所述絮凝沉淀系统包括依次设置的管道混合器和絮凝沉淀装置，所述絮凝沉淀装置包括密封壳体，在所述密封壳体内部设有环形溢流堰、中心管和布料管，所述布料管设置在所述中心管的内部，在所述中心管的底部设有伞型挡板，在所述密封壳体的顶部设有排气口，在所述密封壳体的侧壁设有出水口和进料口，所述出水口与所述环形溢流堰连通，所述进料口与所述布料管连通，在所述密封壳体的底部设有出渣口。
  19. 根据权利要求14、15或18所述的系统，其特征在于，还包括浓盐水储罐，在所述浓盐水储罐的顶部设有水封口，所述排气口通过管道与所述浓盐水储罐的水封口连接。
  20. 根据权利要求13所述的系统，其特征在于，所述干化装置为薄层干化机或低温除湿干化机。
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