CN106179196A - A kind of petrochemical wastewater process adsorbent and preparation method thereof - Google Patents

A kind of petrochemical wastewater process adsorbent and preparation method thereof Download PDF

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CN106179196A
CN106179196A CN201610555322.1A CN201610555322A CN106179196A CN 106179196 A CN106179196 A CN 106179196A CN 201610555322 A CN201610555322 A CN 201610555322A CN 106179196 A CN106179196 A CN 106179196A
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preparation
adsorbent
modified
rectorite
meerschaum
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CN106179196B (en
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叶澄
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CITIC National Chemical Co Ltd
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Wenzhou Hongchengxiang Technology Co Ltd
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Priority to CN201810281434.1A priority patent/CN108439523B/en
Priority to CN201810281432.2A priority patent/CN108421537B/en
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    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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    • 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)

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Abstract

The invention provides the preparation method of a kind of petrochemical wastewater process adsorbent, concrete steps include: the preparation of (1) composite granule gel；(2) preparation of modified compound adsorbent；(3) preparation of magnetic coupling crosslinking adsorbent；Adsorbent of the present invention be by property of modified rectorite and modified meerschaum carry out compound based on adsorbent material, wherein, rectorite and meerschaum introduce organic group on its surface after being modified, its surface nature of extreme enrichment, improve its absorption property；And rectorite and meerschaum are used in combination, playing respective strong point, synergism, the alternative organic and inorganic pollution adsorbing variety classes different with molecular size also substantially increases its absorption property, is greatly expanded its range of application；It addition, adsorbent of the present invention is owing to having magnetic, after absorption, described adsorbent thoroughly can reclaim under interior magnetic field at 20 minutes, it is not necessary to filters, settle, the extra process such as be centrifuged.

Description

A kind of petrochemical wastewater process adsorbent and preparation method thereof
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of petrochemical wastewater process adsorbent and system thereof Preparation Method.
Background technology
Along with expanding economy, the chemical plant of various places gets more and more, the focus being treated as all circles' concern of trade effluent, Traditional plating, process hides, Treatment of Metal Surface, printing and dyeing, petrochemical industry and the wastewater discharge containing other organic pollutions increase day by day Add.
Petrochemical industry is the important component part of chemical industry, plays an important role in the development of national economy, is China One of pillar industry department.Petrochemical industry refers to oil and natural gas as raw material, produces oil product and petrochemicals Processing industry.Oil product also known as oil product, mainly include various fuel oil (gasoline, kerosene, diesel oil etc.) and lubricating oil and Liquefied petroleum gas, oil coke, paraffin, Colophonium etc..The course of processing producing these products is commonly referred to as petroleum refining, is called for short refining Oil.The further chemical process of raw oil that petrochemicals provide with oil refining process obtains.Produce the of petrochemicals One step is that gentle to raw oil (such as propane, gasoline, diesel oil etc.) crack, and generates with ethylene, propylene, butadiene, benzene, first Benzene, dimethylbenzene are the basic chemical raw materials of representative.Second step is to produce multiple Organic Chemicals (about with basic chemical raw materials 200 kinds) and synthetic material (plastics, synthetic fibers, synthetic rubber).The production of this two steps product belongs to the scope of petrochemical industry. Organic Chemicals continues processing can prepare the chemical products of more multi items, is not belonging to the scope of petrochemical industry traditionally.Having In a little data, with natural gas, light gasoline, heavy oil for Material synthesis ammonia, carbamide, even produce nitric acid and also list petrochemical industry in.Existing Its thorough process can not just be discharged it by some petrochemical wastewaters when processing, and causes the pollution of environment, waste resource Pollute environment simultaneously.
Adsorption treatment technology is the technology of a kind of simple and effective process waste water, containing heavy metal ion industrial wastewater, dye The process of material waste water, petrochemical wastewater etc. is widely used.At present, the active charcoal of Industrial Wastewater Treatment common technology adsorbs, boiling Stone exchange etc..Activated carbon is because of features such as it are expensive, regeneration is complicated, it is difficult to large-scale use.
Rectorite Mineral Material is natural product, has the good compatibility with environment, is a kind of ring quite having application prospect Border material, can use as adsorbent.Compared with activated carbon, rectorite has inexpensive, high adsorption capacity, abundance and can be again The advantages such as natural disposition.Containing bigger water-wetted surface in the crystal structure of rectorite, demonstrate good hydrophilic in aqueous And high dispersion.In waste water processes and former water burst Pollution reparation is put into practice, organic in order to improve rectorite absorption Ability, people often use quaternary ammonium salt etc. that it is carried out organic modification, are prepared as organic rectorite.And meerschaum is a kind of rich Fibrous magnesium silicate clay mineral, has the advantages that bigger specific surface area, adsorptivity are good, and its price is less than conventional work Property charcoal commercially available price, meerschaum become waste water process study hotspot.But owing to meerschaum adsorption treatment waste water is difficult to back Receiving, regenerate difficulty, be unfavorable for carrying out industrialization, hinder meerschaum promotes the use of scope.Therefore, meerschaum is used to develop honest and clean Valency, efficient novel absorption material also are used it for processing industrial wastewater, have important practical significance.
Summary of the invention
It is extensive that the technical problem to be solved is to provide a kind of raw material sources, and preparation technology is simple, adsorption capacity Height, processing cost is low, it is easy to adsorbent of recovery and preparation method thereof,.
For solving the problems referred to above, the technical solution used in the present invention is:
The preparation method of a kind of petrochemical wastewater process adsorbent, comprises the steps:
(1) preparation of composite granule gel: the modified meerschaum powder body taking 15-30 part property of modified rectorite powder body and 20-40 part divides Dissipate in the solvent of 100-180 part, and ultrasonic vibration 1-2h at room temperature, then heat to 65-75 DEG C, be slowly added dropwise 20-30 The tetraethyl orthosilicate of part, continues stirring to solution and becomes solid phase；It is solid to mass conservation, at 100-110 DEG C with distilled water wash It is dried 3-6 hour, obtains composite granule gel；
(2) preparation of modified compound adsorbent: modified composite granule gel step (1) obtained joins the season of 10-15 part Mixing and stirring in ammonium salt four cohesive surface activating agent, the chitosan of 6-12 part and 50-80 part toluene solvant, then will mixing Thing transfers in politef hydrothermal reaction kettle hydro-thermal reaction 6-10h at 80-120 DEG C, and reaction end is centrifuged, washes Wash, dry, i.e. obtain modified compound adsorbent；
(3) preparation of magnetic coupling crosslinking adsorbent: the modified compound adsorbent that step (2) obtains is joined 30-40 part In mixed molysite solution, at N2Under protection, under the conditions of 40 DEG C, stirring reaction 20-30 min i.e. obtains described petrochemical wastewater Process adsorbent.
Wherein, in described (2), the preparation method of quaternary ammonium salt four cohesive surface activating agent is: at the 250mL tri-equipped with condensing tube In mouth flask, adding dehydrated alcohol 40mL, ethylenediamine 4.5g, room temperature carries out magnetic agitation, adds epoxy chloropropionate with 10/min Alkane 34.7g, 50 DEG C of back flow reaction 4h after dropping, obtain four cohesive surface surfactant intermediate, for faint yellow after decompression distillation Translucent thick liquid, takes this intermediate 20g, adds dehydrated alcohol and deionized water mixed solution 40mL that volume ratio is 1:l For solvent, then drip 7.9gN, N-dimethyl dodecyl base tertiary amine, it is warming up to 80 DEG C, reacts 1h, decompression distillation, recrystallization, very The empty acquisition white powdery solids that is dried is quaternary ammonium salt four cohesive surface activating agent.
The modifying agent that described property of modified rectorite powder body is used is for selected from ten alkyl trimethyl phosphonium bromides, ten alkyl trimethyls One in phosphorus chloride and cetyl triphenylphosphonium chloride.
The modifying agent that described modified meerschaum powder body is used is for from TEPA, triethylene tetramine, ethylenediamine or second One in ethylenediamine tetraacetic acid (EDTA).
After adding mixed molysite solution in described step (3), being slowly added dropwise 1-2 part concentration during stirring is 28% Ammonia, ammonia finishes and is warming up to 40 DEG C again.
Described mixed molysite be mol ratio be the FeSO of 1:1.5-2.54·7H2O and FeC13·6H2The mixture of O.
In described step (1), solvent is in toluene, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, oxolane One or more.
The technique effect of the present invention is: (1) adsorbent of the present invention is to be combined with property of modified rectorite and modified meerschaum Based on adsorbent material, wherein, rectorite and meerschaum be modified after its surface introduce organic group, extreme enrichment Its surface nature, improves its absorption property；And rectorite and meerschaum are used in combination, play respective strong point, collaborative Effect, the alternative organic and inorganic pollution adsorbing variety classes different with molecular size also substantially increases its adsorptivity Can, it is greatly expanded its range of application；It addition, the present invention uses quaternary ammonium salt four cohesive surface activating agent and chitosan torr tired to modification It is modified that stone and modified meerschaum complex carry out secondary cross-linking so that composite surface inlays the biggest organic of molecular weight further Group, improves it and replaces performance and absorption property, improve its stability and intensity, enables gained adsorbent to stablize and efficient Adsorption removal petrochemical wastewater.
(2) method that adsorbent of the present invention uses hydro-thermal reaction when carrying out twice-modified, use the method can be fabulous The active group of modifying agent is anchored on property of modified rectorite and modified meerschaum complex, and sufficiently stable.
(3) adsorbent of the present invention is owing to having magnetic, and after absorption, described adsorbent can be under 20 minutes interior magnetic fields Thoroughly reclaim, it is not necessary to filter, settle, the extra process such as be centrifuged.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is further elaborated:
Embodiment 1
The preparation method of a kind of petrochemical wastewater process adsorbent, comprises the steps:
(1) preparation of composite granule gel: take 15 part of ten alkyl trimethyl phosphonium bromide property of modified rectorite powder body and 20 part of four ethylene Five amine modified meerschaum powder body are scattered in the toluene of 100 parts, and ultrasonic vibration 1h at room temperature, then heat to 65 DEG C, slow The tetraethyl orthosilicate of slow dropping 20 parts, continues stirring to solution and becomes solid phase；It is solid to mass conservation with distilled water wash, 100 DEG C are dried 3 hours, obtain composite granule gel；
(2) preparation of modified compound adsorbent: modified composite granule gel step (1) obtained joins the quaternary ammonium salt of 10 parts Mixing and stirring in four cohesive surface activating agents, the chitosan of 6 parts and 50 parts of toluene solvants, then transfers to gather by mixture In tetrafluoroethene hydrothermal reaction kettle at 80 DEG C hydro-thermal reaction 6h, reaction end be centrifuged, wash, dry, i.e. obtain modification Compound adsorbent；
(3) preparation of magnetic coupling crosslinking adsorbent: the modified compound adsorbent that step (2) obtains is joined the mixing of 30 parts In iron salt solutions, at N2Under protection, being slowly added dropwise 1 part of concentration during stirring is the ammonia of 28%, stirs under the conditions of 40 DEG C Mix reaction 20 min and i.e. obtain described petrochemical wastewater process adsorbent.
Embodiment 2
The preparation method of a kind of petrochemical wastewater process adsorbent, comprises the steps:
(1) preparation of composite granule gel: take 30 part of ten alkyl trimethyl phosphorus chloride property of modified rectorite powder body and 20-40 part three second Alkene tetramine modified meerschaum powder body is scattered in the DMF of 180 parts, and ultrasonic vibration 2h at room temperature, then It is warming up to 75 DEG C, is slowly added dropwise the tetraethyl orthosilicate of 30 parts, continue stirring to solution and become solid phase；It is solid to distilled water wash Mass conservation, is dried 3 hours at 110 DEG C, obtains composite granule gel；
(2) preparation of modified compound adsorbent: modified composite granule gel step (1) obtained joins the quaternary ammonium salt of 15 parts Mixing and stirring in four cohesive surface activating agents, the chitosan of 12 parts and 80 parts of toluene solvants, then transfers to mixture In politef hydrothermal reaction kettle at 120 DEG C hydro-thermal reaction 10h, reaction end be centrifuged, wash, dry, i.e. obtain Modified compound adsorbent；
(3) preparation of magnetic coupling crosslinking adsorbent: the modified compound adsorbent that step (2) obtains is joined the mixing of 40 parts In iron salt solutions, at N2Under protection, being slowly added dropwise 2 parts of concentration during stirring is the ammonia of 28%, stirs under the conditions of 40 DEG C Mix reaction 27 min and i.e. obtain described petrochemical wastewater process adsorbent.
Embodiment 3
The preparation method of a kind of petrochemical wastewater process adsorbent, comprises the steps:
(1) preparation of composite granule gel: take 20 parts of cetyl triphenylphosphonium chloride property of modified rectorite powder body and 30 parts of second two Amine modified meerschaum powder body is scattered in the N,N-dimethylacetamide of 140 parts, and ultrasonic vibration 1.5h at room temperature, then rises Temperature, to 70 DEG C, is slowly added dropwise the tetraethyl orthosilicate of 25 parts, continues stirring to solution and becomes solid phase；It is solid to matter with distilled water wash Measure constant, be dried 5 hours at 105 DEG C, obtain composite granule gel；
(2) preparation of modified compound adsorbent: modified composite granule gel step (1) obtained joins the quaternary ammonium salt of 12 parts Mixing and stirring in four cohesive surface activating agents, the chitosan of 9 parts and 70 parts of toluene solvants, then transfers to gather by mixture In tetrafluoroethene hydrothermal reaction kettle at 100 DEG C hydro-thermal reaction 8h, reaction end be centrifuged, wash, dry, i.e. obtain modification Compound adsorbent；
(3) preparation of magnetic coupling crosslinking adsorbent: the modified compound adsorbent that step (2) obtains is joined the mixing of 35 parts In iron salt solutions, at N2Under protection, being slowly added dropwise 1.5 parts of concentration during stirring is the ammonia of 28%, under the conditions of 40 DEG C Stirring reaction 25 min i.e. obtain described petrochemical wastewater process adsorbent.
Embodiment 4
The preparation method of a kind of petrochemical wastewater process adsorbent, comprises the steps:
(1) preparation of composite granule gel: take 25 part of ten alkyl trimethyl phosphonium bromide property of modified rectorite powder body and 35 parts of ethylenediamines Tetraacetic acid modified meerschaum powder body is scattered in the oxolane of 160 parts, and ultrasonic vibration 1.8h at room temperature, then heats to 70 DEG C, it is slowly added dropwise the tetraethyl orthosilicate of 28 parts, continues stirring to solution and become solid phase；It is solid to quality not with distilled water wash Become, be dried 5 hours at 110 DEG C, obtain composite granule gel；
(2) preparation of modified compound adsorbent: modified composite granule gel step (1) obtained joins the quaternary ammonium salt of 14 parts Mixing and stirring in four cohesive surface activating agents, the chitosan of 10 parts and 70 parts of toluene solvants, then transfers to mixture In politef hydrothermal reaction kettle at 110 DEG C hydro-thermal reaction 9h, reaction end be centrifuged, wash, dry, i.e. changed Property compound adsorbent；
(3) preparation of magnetic coupling crosslinking adsorbent: the modified compound adsorbent that step (2) obtains is joined the mixing of 38 parts In iron salt solutions, at N2Under protection, being slowly added dropwise 1.5 parts of concentration during stirring is the ammonia of 28%, under the conditions of 40 DEG C Stirring reaction 25 min i.e. obtain described petrochemical wastewater process adsorbent.
Embodiment 5
The preparation method of a kind of petrochemical wastewater process adsorbent, comprises the steps:
(1) preparation of composite granule gel: take 18 part of ten alkyl trimethyl phosphorus chloride property of modified rectorite powder body and 25 parts of ethylenediamines Tetraacetic acid modified meerschaum powder body is scattered in the N,N-dimethylacetamide of 130 parts, and ultrasonic vibration 1h at room temperature, then It is warming up to 75 DEG C, is slowly added dropwise the tetraethyl orthosilicate of 25 parts, continue stirring to solution and become solid phase；It is solid to distilled water wash Mass conservation, is dried 4 hours at 105 DEG C, obtains composite granule gel；
(2) preparation of modified compound adsorbent: modified composite granule gel step (1) obtained joins the quaternary ammonium salt of 12 parts Mixing and stirring in four cohesive surface activating agents, the chitosan of 9 parts and 60 parts of toluene solvants, then transfers to gather by mixture In tetrafluoroethene hydrothermal reaction kettle at 90 DEG C hydro-thermal reaction 10h, reaction end be centrifuged, wash, dry, i.e. obtain modification Compound adsorbent；
(3) preparation of magnetic coupling crosslinking adsorbent: the modified compound adsorbent that step (2) obtains is joined the mixing of 33 parts In iron salt solutions, at N2Under protection, being slowly added dropwise 1.5 parts of concentration during stirring is the ammonia of 28%, under the conditions of 40 DEG C Stirring reaction 22 min i.e. obtain described petrochemical wastewater process adsorbent.
Comparative example 1
Preparation method is same as in Example 1, and unique difference is that raw material uses single meerschaum.
Comparative example 2
Preparation method is same as in Example 1, and unique difference is in step (2) that modified feedstock is lived only with quaternary ammonium salt four cohesive surface Property agent.
Comparative example 3
Preparation method is same as in Example 1, and unique difference is that the hydro-thermal reaction of step (2) changes normal pressure water-bath into.
Adsorption experiment I: embodiment 1-5 and comparative example 1-3 contain the absorption of waste water to simulation.
Using the absorbent particles after activation to process simulated oily wastewater, simulation oil-containing water sample major parameter is as follows: COD is dense Degree is 1500.Omg L-1, oil concentration be 982.0mg L-1, water sampling 40mL.
Consumption and the adsorption conditions of adsorbent include: the consumption of absorbent particles is 25g/L, through meter 1g adsorbent, absorption Temperature is 40 DEG C, and adsorption time is 120min, and experimental result see table 1.
Can be drawn by table 1, the adsorbent of embodiment 1-5 all demonstrates good suction to COD in petrochemical wastewater and oil Attached performance, and it is better than the adsorbent of comparative example 1-3.
Finally it is noted that the foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, Although being described in detail the present invention with reference to previous embodiment, for a person skilled in the art, it still may be used So that the technical scheme described in foregoing embodiments to be modified, or wherein portion of techniques feature is carried out equivalent. All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included in the present invention's Within protection domain.

Claims (8)

1. the preparation method of a petrochemical wastewater process adsorbent, it is characterised in that comprise the steps:
(1) preparation of composite granule gel: the modified meerschaum powder body taking 15-30 part property of modified rectorite powder body and 20-40 part divides Dissipate in the solvent of 100-180 part, and ultrasonic vibration 1-2h at room temperature, then heat to 65-75 DEG C, be slowly added dropwise 20-30 The tetraethyl orthosilicate of part, continues stirring to solution and becomes solid phase；It is solid to mass conservation, at 100-110 DEG C with distilled water wash It is dried 3-6 hour, obtains composite granule gel；
(2) preparation of modified compound adsorbent: modified composite granule gel step (1) obtained joins the season of 10-15 part Mixing and stirring in ammonium salt four cohesive surface activating agent, the chitosan of 6-12 part and 50-80 part toluene solvant, then will mixing Thing transfers in politef hydrothermal reaction kettle hydro-thermal reaction 6-10h at 80-120 DEG C, and reaction end is centrifuged, washes Wash, dry, i.e. obtain modified compound adsorbent；
(3) preparation of magnetic composite adsorbent: the modified compound adsorbent that step (2) obtains is joined the mixing of 30-40 part In iron salt solutions, at N2Under protection, under the conditions of 40 DEG C, stirring reaction 20-30 min i.e. obtains the process of described petrochemical wastewater Use adsorbent.
Preparation method the most according to claim 1, it is characterised in that quaternary ammonium salt four cohesive surface activating agent in described (2) Preparation method is: equipped with in the 250mL there-necked flask of condensing tube, adding dehydrated alcohol 40mL, ethylenediamine 4.5g, room temperature is carried out Magnetic agitation, adds epoxychloropropane 34.7g, 50 DEG C of back flow reaction 4h after dropping with 10/min, obtains after decompression distillation To four cohesive surface surfactant intermediate, for faint yellow translucent thick liquid, taking this intermediate 20g, adding volume ratio is 1:l's Dehydrated alcohol and deionized water mixed solution 40mL are solvent, then drip 7.9gN, N-dimethyl dodecyl base tertiary amine, are warming up to 80 DEG C, reacting 1h, decompression distillation, recrystallization, vacuum drying obtains white powdery solids and is quaternary ammonium salt four cohesive surface activity Agent.
Preparation method the most according to claim 1, it is characterised in that the modifying agent that described property of modified rectorite powder body is used For the one in ten alkyl trimethyl phosphonium bromides, ten alkyl trimethyl phosphorus chloride and cetyl triphenylphosphonium chloride.
Preparation method the most according to claim 1, it is characterised in that the modifying agent that described modified meerschaum powder body is used For the one in TEPA, triethylene tetramine, ethylenediamine or ethylenediaminetetraacetic acid.
Preparation method the most according to claim 1, it is characterised in that after adding mixed molysite solution in described step (3), Being slowly added dropwise 1-2 part concentration during stirring is the ammonia of 28%, and ammonia finishes and is warming up to 40 DEG C again.
Preparation method the most according to claim 1, it is characterised in that described mixed molysite be mol ratio be 1:1.5- The FeSO of 2.54·7H2O and FeC13·6H2The mixture of O.
Preparation method the most according to claim 1, it is characterised in that in described step (1), solvent is toluene, N, N-diformazan One or more in base Methanamide, DMAC N,N' dimethyl acetamide, oxolane.
8. the adsorbent that method described in an any one of claim 1-7 prepares.
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