CN115869579A - Curing method and curing device for aluminum chlorohydrate waste ionic liquid - Google Patents

Curing method and curing device for aluminum chlorohydrate waste ionic liquid Download PDF

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Publication number
CN115869579A
CN115869579A CN202111154809.6A CN202111154809A CN115869579A CN 115869579 A CN115869579 A CN 115869579A CN 202111154809 A CN202111154809 A CN 202111154809A CN 115869579 A CN115869579 A CN 115869579A
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ionic liquid
chloroaluminate
waste
waste ionic
curing
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CN115869579B (en
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莫馗
程学文
张宾
高凤霞
李海龙
王珺
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention discloses a curing method and a curing device for chloroaluminate waste ionic liquid. The curing method comprises the following steps: carrying out digestion reaction on chloroaluminate waste ionic liquid and water under the condition of continuous stirring, wherein the volume ratio of the chloroaluminate waste ionic liquid to the water is 1:0.1-0.6. The solidifying device comprises a vacuum kneader which is used for mixing the chloroaluminate waste ionic liquid with water under the stirring condition to carry out digestion reaction to form solid substances. The method provided by the invention is safe and environment-friendly, has simple treatment process, and can efficiently reduce the generation amount of dangerous solid wastes and reduce the treatment operation cost.

Description

Curing method and curing device for chloroaluminate waste ionic liquid
Technical Field
The invention belongs to the technical field of chemical industry and environmental protection, relates to a hazardous waste treatment process, and particularly relates to a method and a device for curing chloroaluminate waste ionic liquid.
Background
The improvement of the environmental protection standard in China makes the upgrading of the oil quality a necessary choice. C4 catalytic alkylation is an important process for producing clean high octane gasoline blending components (i.e., alkylate). The traditional alkylation technology is mainly divided into a sulfuric acid method and a hydrofluoric acid method, but both the two methods have the problems of serious equipment corrosion, environmental pollution and the like which are difficult to solve, and the wide popularization and application of the alkylation technology are greatly limited. The ionic liquid is a composite salt consisting of alkyl quaternary ammonium cation and composite anion, and the novel alkylation process using the composite ionic liquid as an alkylation reaction catalyst is far superior to the traditional method in terms of product conversion efficiency, process safety and environmental friendliness, and is already widely adopted by newly-built alkylation devices.
The composite ionic liquid catalyst mainly comprises the following components: anhydrous aluminum chloride (AlCl 3), triethylamine hydrochloride (Et 3 NHCl), and transition metal salts (such as Cu2Cl 2). During the alkylation reaction, some acid soluble oil impurities are produced. In order to keep the catalyst in the reaction system to have higher activity and selectivity, when the ionic liquid contains higher acid-soluble oil, fresh ionic liquid needs to be added to keep the catalytic activity, and in the ionic liquid regeneration process, redundant ionic liquid is discharged after concentration and extraction, so that waste ionic liquid is finally formed.
Among the main components of the waste ionic liquid of the chloroaluminate, part of the ionic liquid catalyst with weakened activity; partially salts formed by inactivating the ionic liquid; part of the acid-soluble oil is formed in the alkylation process, and the acid-soluble oil is a dangerous solid waste with high activity, high acidity, high oil content and high salt content, which can cause huge potential safety hazard in direct discharge and storage and must be harmlessly treated.
Chinese patent publication No. CN 105056587A reports a production process for waste ionic liquid treatment. The waste ionic liquid and the high-concentration NaOH solution are fully mixed in the pipeline mixer to react, the alkaline solution containing the metal solid slag is conveyed to a horizontal spiral centrifugal machine for liquid-solid separation, the separated metal solid slag is settled, dehydrated, dried and discharged, and the obtained alkaline clear liquid is mixed with fresh alkali liquor to carry out acid-alkali neutralization reaction. And collecting the dissolved hydrocarbon carried by the ionic liquid into a dirty oil recovery tank. The existing process flow formed according to this patent is: waste ionic liquid is clear, neutralized, precipitated, dehydrated and dried, and each ton of waste ionic liquid generates 1.7 to 1.8 tons of absolute dry solid, and the solid components are as follows: 26% of Al (OH) 3, 8% of Cu (OH) 2, 65% of NaCl and 1% of petroleum. The solid belongs to dangerous waste, the disposal cost reaches 3000-5000 yuan/ton, and the operation cost is very high.
Aiming at the process condition of the waste ionic liquid at present, a novel waste ionic liquid treatment method is urgently needed to be developed so as to achieve the purposes of reducing the amount of dangerous solid waste and reducing the operation cost.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a curing method and a curing device for chloroaluminate waste ionic liquid.
To this end, the first aspect of the invention provides a method for curing the chloroaluminate waste ionic liquid.
As a specific embodiment of the present invention, the curing method comprises the steps of:
carrying out digestion reaction on chloroaluminate waste ionic liquid and water under the condition of continuous stirring, wherein the volume ratio of the chloroaluminate waste ionic liquid to the water is 1:0.1-0.6.
Preferably, the volume ratio of the chloroaluminate waste ionic liquid to water is 1:0.2-0.4.
Preferably, the continuous stirring is carried out at a speed of 100 to 900rpm for 5 to 60min.
Preferably, the continuous stirring is carried out at a speed of 200-800rpm for 10-45min.
Preferably, solid substances are formed after the chloroaluminate waste ionic liquid is subjected to digestion reaction, and preferably, the solid substances are granular dry solid substances.
The inventor finds that after the waste ionic liquid is digested by a small amount of water, salts in the waste ionic liquid are resolved and dissolved in the water, but the waste ionic liquid is quickly crystallized and separated out due to limited solubility and is wrapped with other substances to form dry solidified particles.
Optionally, the curing method further comprises: and leading out hydrochloric acid mist generated in the digestion reaction and absorbing the hydrochloric acid mist by using an alkaline absorption liquid.
Preferably, the alkaline absorption liquid is an aqueous solution of NaOH, and the concentration thereof is preferably 5 wt% to 20 wt%.
Preferably, the chloroaluminate waste ionic liquid is a waste catalyst produced by catalyzing carbon four with chloroaluminate ionic liquid to produce alkylate oil.
The active components of the aluminum chlorohydrate ionic liquid waste catalyst mainly comprise triethylamine hydrochloride, aluminum chloride, copper chloride and the like, and the other components mainly comprise acid-soluble hydrocarbon (namely acid-soluble oil).
The method for curing the chloroaluminate waste ionic liquid is mainly realized by the following steps:
firstly, introducing chloroaluminate waste ionic liquid into a reaction vessel from a storage vessel through a pump;
secondly, mixing chloroaluminate waste ionic liquid with a proper amount of water in a reaction vessel under the condition of uninterrupted proper stirring for proper digestion reaction until the residual activity of the waste ionic liquid is completely eliminated and a granular dry solid substance is formed;
thirdly, heat is released and hydrochloric acid mist is generated in the digestion reaction process, and the acid gas needs to be led out to an absorber for absorption;
and fourthly, discharging the granular dry solid substances from the reaction container, conveying the granular dry solid substances to a packing unit, and performing subsequent treatment after packing.
A second aspect of the present invention provides a curing apparatus for carrying out the curing method of the first aspect.
As a specific embodiment of the present invention, the curing device includes:
and the vacuum kneader is used for mixing the chloroaluminate waste ionic liquid with water under the stirring condition to carry out digestion reaction.
Preferably, the curing device further comprises: the device comprises a waste ionic liquid storage tank, an acid gas absorber, a conveying belt and a packaging machine, wherein the waste ionic liquid storage tank is used for storing and supplying chloroaluminate waste ionic liquid to the vacuum kneader;
the acid gas absorber is used for absorbing hydrochloric acid mist from the vacuum kneader;
the packing machine and the conveyer belt are sequentially connected with the vacuum kneading machine and are used for conveying and packing the granular dry solid substances from the vacuum kneading machine.
Preferably, the curing device further comprises a water storage tank.
The operation process of the curing device for the aluminum chloroaluminate waste ionic liquid comprises the following steps:
the waste ionic liquid is homogenized in a waste ionic liquid storage tank 1 and then is sent to a vacuum kneader 3 through a feeding metering pump 2, meanwhile, clear water in a water storage tank 4 is also sent to the vacuum kneader 3 through a clear water metering pump 5, the waste ionic liquid and clear water with a certain volume ratio in the vacuum kneader 3 are subjected to moderate digestion reaction under the stirring condition of a certain rotating speed, after the reaction is carried out for a certain time, formed granular dry solid substances are discharged from the vacuum kneader 3 and are conveyed to a packing machine 9 through a conveying belt 8, and the subsequent treatment is carried out after the packing. While heat is released and hydrochloric acid mist is generated during the digestion reaction in the vacuum kneader 3, the generated acid gas needs to be sucked into an acid gas absorber 7 for neutralization and absorption through a suction pump 6 at the top of the vacuum kneader for neutralization and absorption, and an alkaline absorption liquid exists in the acid gas absorber 7.
The above raw materials in the present invention may be prepared by themselves or may be obtained commercially, and the present invention is not particularly limited thereto.
Through the technical scheme: the invention realizes the following beneficial effects:
the waste ionic liquid is subjected to moderate digestion reaction with a proper amount of water, and is directly solidified, so that hazardous components in the ionic liquid generate common solid waste residues which are easy to dispose, safety and environmental protection are realized, and environmental pollution and potential safety hazards caused by large-scale storage and discharge of the waste ionic liquid are avoided; the treatment process is simple, and the amount of dangerous solid waste can be efficiently reduced, and the treatment operation cost can be reduced.
Drawings
Fig. 1 shows a schematic structural view of a curing apparatus of the present invention.
Description of reference numerals:
1. the device comprises a waste ionic liquid storage tank, 2, a feeding metering pump, 3, a vacuum kneader, 4, a water storage tank, 5, a clean water metering pump, 6, an air suction pump, 7, an acid gas absorber, 8, a conveying belt, 9 and a packaging machine.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
FIG. 1 shows one embodiment of a curing apparatus of the present invention. As shown in fig. 1, the solidifying device of the present invention comprises a waste ionic liquid storage tank 1, a feeding metering pump 2, a vacuum kneader 3, a water storage tank 4, a clean water metering pump 5, an air suction pump 6, an acid gas absorber 7, a conveyer belt 8 and a packing machine 9.
The waste ionic liquid storage tank 1 is used for storing and supplying chloroaluminate waste ionic liquid to the vacuum kneader 3; the acid gas absorber 7 is used for absorbing hydrochloric acid mist from the vacuum kneader 3; the baler 9 and the conveyor belt 8 are connected in sequence with the vacuum kneader 3 for transporting and baling the granular dry solid substance from the vacuum kneader 3.
The curing method of the invention is mainly realized by the following technical scheme:
firstly, aluminum chlorohydrate waste ionic liquid is stored in a waste ionic liquid storage tank 1, and the waste ionic liquid enters a vacuum kneader 3 through a feeding metering pump 2; meanwhile, clear water also enters the vacuum kneading machine 3 from the water storage tank 4 through the clear water metering pump 5;
secondly, under the condition of uninterrupted stirring, mixing the waste ionic liquid and a proper amount of water in a vacuum kneader 3 for proper digestion reaction until the waste ionic liquid forms a granular dry solid substance;
thirdly, heat is released and hydrochloric acid mist is generated in the digestion reaction process, and the acid gas is required to be led out to an acid gas absorber 7 through an air suction pump 6 for absorption;
and fourthly, discharging the granular dry solid substance from the vacuum kneader 3, conveying the granular dry solid substance to a packing machine 9 through a conveying belt 8, and carrying out subsequent treatment after packing.
The technological process of the curing device is as follows:
the waste ionic liquid is homogenized in a waste ionic liquid storage tank 1 and then is sent to a vacuum kneader 3 through a feeding metering pump 2, meanwhile, clear water in a water storage tank 4 is also sent to the vacuum kneader 3 through a clear water metering pump 5, the waste ionic liquid and clear water in a certain volume ratio in the vacuum kneader 3 are subjected to moderate digestion reaction under the stirring condition of a certain rotating speed, after the reaction is carried out for a certain time, formed granular dry solid substances are discharged from the vacuum kneader 3 and are conveyed to a packing machine 9 through a conveying belt 8, and the subsequent treatment is carried out after the packing. While the digestion reaction in the vacuum kneader 3 is exothermic and hydrochloric acid mist is generated, the generated acid gas is sucked into an acid gas absorber 7 through a suction pump 6 at the top of the vacuum kneader for neutralization and absorption, and an alkaline absorption liquid is contained in the acid gas absorber 7.
The first embodiment is as follows: 100ml of chloroaluminate waste ionic liquid of a petrochemical enterprise is taken and placed in a reaction container, 20ml of water is dropwise added into the reaction container under the condition of uninterrupted stirring, the waste ionic liquid and the water are mixed to carry out moderate digestion reaction, the stirring speed is 600rpm, and the stirring time is 20min until the waste ionic liquid forms granular dry solid matters. The acid gas generated is absorbed by 10% NaOH solution.
Example two: 100ml of chloroaluminate waste ionic liquid of a petrochemical enterprise is taken and placed in a reaction container, 35ml of water is dropwise added into the reaction container under the condition of uninterrupted stirring, the waste ionic liquid and the water are mixed to carry out moderate digestion reaction, the stirring speed is 300rpm, and the stirring time is 40min until the waste ionic liquid forms granular dry solid matters. The acid gas generated is absorbed by using 20% NaOH solution.
Example three: taking 100ml of chloroaluminate waste ionic liquid of a petrochemical enterprise, mixing the waste ionic liquid with 15ml of water in a reaction vessel under the condition of uninterrupted stirring for proper digestion reaction, wherein the stirring speed is 300rpm, the stirring time is 40min, and the waste ionic liquid is still in a thin paste shape and does not form a dry solid matter.
Example four: taking 100ml of chloroaluminate waste ionic liquid of a petrochemical enterprise, mixing the waste ionic liquid with 50ml of water in a reaction container under the condition of uninterrupted stirring for digestion reaction, wherein the stirring speed is 300rpm, the stirring time is 40min, and the waste ionic liquid is in a thin paste state and does not form dry solid matters.
Comparing the first and second examples with the third and fourth examples, it is found that when the volume ratio of the aluminum chloroaluminate waste ionic liquid to water is too large or too small, the waste ionic liquid is solidified to be in a thin paste or paste state, and a dry solid substance is not formed.
Further, when the volume ratio of the chloroaluminate waste ionic liquid to water is 1: when the concentration is 0.2-0.4, the aluminum chlorohydrate waste ionic liquid is solidified to form dry solid matters.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or the value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88, 8230, and 69 to 71 and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The present invention can be modified within the scope of the claims as prescribed, and the technical solution of the present invention can be modified without departing from the scope and spirit of the present invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. The curing method of the chloroaluminate waste ionic liquid is characterized by comprising the following steps:
carrying out digestion reaction on chloroaluminate waste ionic liquid and water under the condition of continuous stirring, wherein the volume ratio of the chloroaluminate waste ionic liquid to the water is 1:0.1-0.6.
2. The curing method of claim 1, wherein the volume ratio of chloroaluminate waste ionic liquid to water is 1:0.2-0.4.
3. The curing process according to claim 1 or 2, wherein the continuous stirring is carried out at a speed of 100-900rpm for 5-60min.
4. The curing process according to claim 1 or 2, wherein the continuous stirring is carried out at a speed of 200-800rpm for 10-45min.
5. The curing method according to claim 1 or 2, wherein the chloroaluminate waste ionic liquid forms a solid substance after digestion reaction, and preferably, the solid substance is a granular dry solid substance.
6. The curing method of any one of claims 1-3, further comprising:
and leading out hydrochloric acid mist generated in the digestion reaction and absorbing the hydrochloric acid mist by using an alkaline absorption liquid.
7. The curing method according to claim 6, wherein the alkaline absorption liquid is an aqueous NaOH solution, and the concentration of the alkaline absorption liquid is preferably 5-20 wt%.
8. The curing method of any one of claims 1 to 7, wherein the chloroaluminate waste ionic liquid is a waste catalyst produced by catalyzing carbon four to produce alkylate with chloroaluminate ionic liquid.
9. Curing apparatus for carrying out the curing method of any one of claims 1 to 8, characterized in that the curing apparatus comprises:
and the vacuum kneader is used for mixing the chloroaluminate waste ionic liquid with water under the stirring condition to carry out digestion reaction.
10. The curing apparatus of claim 9, further comprising: a waste ionic liquid storage tank, an acid gas absorber, a conveying belt and a packaging machine; wherein the content of the first and second substances,
the waste ionic liquid storage tank is used for storing and supplying chloroaluminate waste ionic liquid to the vacuum kneader;
the acid gas absorber is used for absorbing hydrochloric acid mist from the vacuum kneader;
the packing machine and the conveyer belt are sequentially connected with the vacuum kneading machine and are used for conveying and packing the granular dry solid substances from the vacuum kneading machine.
CN202111154809.6A 2021-09-29 Method and device for solidifying waste chloroaluminate ionic liquid Active CN115869579B (en)

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CN202111154809.6A CN115869579B (en) 2021-09-29 Method and device for solidifying waste chloroaluminate ionic liquid

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Application Number Priority Date Filing Date Title
CN202111154809.6A CN115869579B (en) 2021-09-29 Method and device for solidifying waste chloroaluminate ionic liquid

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CN115869579B CN115869579B (en) 2024-06-04

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11244815A (en) * 1998-03-03 1999-09-14 Taiheiyo Cement Corp Contaminated metal fixing and stabilizing agent and its treatment
US20100129921A1 (en) * 2008-11-26 2010-05-27 Chevron U.S.A., Inc. Monitoring of ionic liquid catalyst deactivation
US20130211175A1 (en) * 2012-02-14 2013-08-15 Chevron U.S.A. Inc. Hydrolysis of used ionic liquid catalyst for disposal
US8575374B1 (en) * 2010-10-21 2013-11-05 Hugh C. DeLong Ionic liquids processing of biomass to reducing sugars and other dehydration products
CN208340703U (en) * 2018-03-01 2019-01-08 中国石油大学(北京) The system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water
CN211035481U (en) * 2019-09-19 2020-07-17 沈阳松辽环境工程有限公司 Handle device for carrying out digestion reaction on chloroaluminate ionic liquid
US20200392029A1 (en) * 2018-03-01 2020-12-17 China University Of Petroleum-Beijing Method and system for treatment of spent chloroaluminate ionic liquid catalyst and alkaline wastewater
CN112705260A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Production method and device of ionic liquid catalyst

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11244815A (en) * 1998-03-03 1999-09-14 Taiheiyo Cement Corp Contaminated metal fixing and stabilizing agent and its treatment
US20100129921A1 (en) * 2008-11-26 2010-05-27 Chevron U.S.A., Inc. Monitoring of ionic liquid catalyst deactivation
US8575374B1 (en) * 2010-10-21 2013-11-05 Hugh C. DeLong Ionic liquids processing of biomass to reducing sugars and other dehydration products
US20130211175A1 (en) * 2012-02-14 2013-08-15 Chevron U.S.A. Inc. Hydrolysis of used ionic liquid catalyst for disposal
CN208340703U (en) * 2018-03-01 2019-01-08 中国石油大学(北京) The system for handling chlorine aluminium acidic ionic liquids dead catalyst and alkaline waste water
US20200392029A1 (en) * 2018-03-01 2020-12-17 China University Of Petroleum-Beijing Method and system for treatment of spent chloroaluminate ionic liquid catalyst and alkaline wastewater
CN211035481U (en) * 2019-09-19 2020-07-17 沈阳松辽环境工程有限公司 Handle device for carrying out digestion reaction on chloroaluminate ionic liquid
CN112705260A (en) * 2019-10-25 2021-04-27 中国石油化工股份有限公司 Production method and device of ionic liquid catalyst

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