CN106179196B - A kind of petrochemical wastewater processing adsorbent and preparation method thereof - Google Patents

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

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CN106179196B
CN106179196B CN201610555322.1A CN201610555322A CN106179196B CN 106179196 B CN106179196 B CN 106179196B CN 201610555322 A CN201610555322 A CN 201610555322A CN 106179196 B CN106179196 B CN 106179196B
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adsorbent
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rectorite
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CN106179196A (en
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侯福顺
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CITIC National Chemical Co Ltd
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CITIC National Chemical Co Ltd
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • 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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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
    • B01J20/26—Synthetic macromolecular compounds
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    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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    • C02F1/00—Treatment of water, waste water, or sewage
    • 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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    • C02F2103/00—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)

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Abstract

The present invention provides a kind of preparation method of petrochemical wastewater processing adsorbent, specific steps include：（1）The preparation of composite granule gel；（2）The preparation of modified compound adsorbent；（3）The preparation of magnetic coupling crosslinking adsorbent；Adsorbent of the present invention be carried out using property of modified rectorite and modified meerschaum it is compound as basic adsorbent material, wherein, rectorite and sepiolite be modified after in its surface introducing organic group, its surface nature of extreme enrichment improves its absorption property；And rectorite and sepiolite are used in combination, and play respective strong point, synergistic effect, and the alternative absorption variety classes organic and inorganic pollution different with molecular size also substantially increases its absorption property, greatly expands its application range；In addition, adsorbent of the present invention, due to having magnetism, after absorption, the adsorbent can thoroughly be recycled at 20 minutes under interior magnetic field, without filtering, settling, the extra process such as centrifuging.

Description

A kind of petrochemical wastewater processing adsorbent and preparation method thereof
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of petrochemical wastewater processing adsorbent and its system Preparation Method.
Background technology
With the development of economy, the chemical plant of various regions is more and more, the hot spot for being treated as all circles' concern of trade effluent, Traditional plating, process hides, Treatment of Metal Surface, printing and dyeing, petrochemical industry and wastewater discharge containing other organic pollutions increasingly increases Add.
Petrochemical industry is the important component of chemical industry, is played an important role in the development of national economy, is China One of pillar industry department.Petrochemical industry refers to using oil and natural gas as raw material, produces oil product and petrochemicals Processing industry.Oil product is also known as oil product, mainly including various fuel oil (gasoline, kerosene, diesel oil etc.) and lubricating oil and Liquefied petroleum gas, oil coke, paraffin, pitch etc..The process for producing these products is commonly referred to as petroleum refining, referred to as refines Oil.Petrochemicals are obtained with the further chemical process of feedstock oil that oil refining process provides.Produce the of petrochemicals One step is that (such as propane, gasoline, diesel oil) gentle to feedstock oil cracks, and is generated with ethylene, propylene, butadiene, benzene, first Benzene, the basic chemical raw materials that dimethylbenzene is representative.Second step is to produce a variety of 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 range of petrochemical industry. Organic Chemicals, which continues processing, can be made the chemical products of more multi items, traditionally be not belonging to the range of petrochemical industry.Having In a little data, as Material synthesis ammonia, urea or even produce nitric acid using natural gas, light petrol, heavy oil and be also included in petrochemical industry.It is existing It in processing cannot thoroughly be handled and just discharged it by some petrochemical wastewaters, lead to the pollution of environment, waste of resource Pollute environment simultaneously.
Adsorption treatment technology is a kind of technology of simple and effective processing waste water, containing heavy metal ion industrial wastewater, dye It is widely used in the processing of material waste water, petrochemical wastewater etc..At present, the active charcoal absorption of Industrial Wastewater Treatment common technology, boiling Stone exchange etc..Activated carbon is because of the features such as its is expensive, regeneration is complicated, it is difficult to large-scale use.
Rectorite Mineral Material is natural products, has good compatibility with environment, is a kind of ring for quite having application prospect Border material can be used as adsorbent.Compared with activated carbon, rectorite has strong inexpensive, adsorption capacity, abundance and can be again The advantages that natural disposition.Containing larger water-wetted surface in the crystal structure of rectorite, good hydrophily is shown in aqueous solution And high dispersion.In wastewater treatment and raw water burst Pollution reparation practice, in order to improve rectorite absorption organic matter Ability, people often carry out organic modification to it using quaternary ammonium salt etc., are prepared into organic rectorite.And sepiolite is a kind of richness Fibrous magnesium silicate clay mineral has the characteristics that larger specific surface area, adsorptivity are good, and price is less than common work The commercially available price of property charcoal, sepiolite have become the research hotspot of wastewater treatment.But since sepiolite adsorption treatment waste water is not easy back It receives, regeneration difficulty, be unfavorable for being industrialized, hinder sepiolite promotes the use of range.Therefore, it is developed using sepiolite honest and clean Valency, efficient novel absorption material simultaneously use it for processing industrial wastewater, have important practical significance.
Invention content
The technical problems to be solved by the invention are to provide that a kind of raw material sources are extensive, and preparation process is simple, adsorption capacity Height, processing cost is low, adsorbent being easily recycled and preparation method thereof,.
To solve the above problems, the technical solution adopted by the present invention is：
A kind of preparation method of petrochemical wastewater processing adsorbent, includes the following steps：
（1）The preparation of composite granule gel：Take the modified meerschaum powder of 15-30 parts of property of modified rectorite powders and 20-40 parts Body is scattered in 100-180 parts of solvent, and ultrasonic vibration 1-2h at room temperature, is then heated to 65-75 DEG C, is slowly added dropwise 20-30 parts of ethyl orthosilicate continues stirring to solution and becomes solid phase；It is washed with distilled water and is solid to mass conservation, in 100- 110 DEG C 3-6 hours dry, obtains composite granule gel；
（2）The preparation of modified compound adsorbent：By step（1）Obtained modified composite powder body gel is added to 10-15 parts Four poly- surfactant of quaternary ammonium salt, be mixed evenly in 6-12 parts of chitosan and 50-80 parts of toluene solvants, then will Mixture is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle the hydro-thermal reaction 6-10h at 80-120 DEG C, reaction terminates to be centrifuged, Washing is dried to get to modified compound adsorbent；
（3）The preparation of magnetic coupling crosslinking adsorbent：By step（2）The modification compound adsorbent of acquisition is added to 30-40 In the mixed molysite solution of part, in N2Under protection, 20-30 min are stirred to react under the conditions of 40 DEG C and obtain the petrochemical industry Use in waste water treatment adsorbent.
Wherein, it is described（2）The preparation method of middle four poly- surfactant of quaternary ammonium salt is：In the 250mL tri- equipped with condenser pipe In mouth flask, absolute ethyl alcohol 40mL, ethylenediamine 4.5g are added in, room temperature carries out magnetic agitation, and epoxy chloropropionate is added in 10 drops/min Alkane 34.7g, 50 DEG C of back flow reaction 4h after being added dropwise, obtains four poly- surfactant-intermediates after vacuum distillation, be faint yellow Translucent thick liquid takes intermediate 20g, and it is 1 to add in volume ratio:The absolute ethyl alcohol of l and deionized water mixed solution 40mL For solvent, then 7.9gN is added dropwise, N- dimethyl dodecyl base tertiary amines are warming up to 80 DEG C, react 1h, are evaporated under reduced pressure, recrystallization, very The dry white powdery solids that obtain of sky are four poly- surfactant of quaternary ammonium salt.
Modifying agent used in the property of modified rectorite powder is selected from ten alkyl trimethyl phosphonium bromides, ten alkyl trimethyls One kind in phosphorus chloride and cetyl triphenylphosphonium chloride.
Modifying agent used in the modified meerschaum powder is from tetraethylenepentamine, triethylene tetramine, ethylenediamine or second One kind in ethylenediamine tetraacetic acid (EDTA).
The step（3）After middle addition mixed molysite solution, 1-2 parts a concentration of 28% are slowly added dropwise during stirring Ammonium hydroxide, ammonium hydroxide finishes is warming up to 40 DEG C again.
The mixed molysite is that molar ratio is 1:The FeSO of 1.5-2.54·7H2O and FeC13·6H2The mixture of O.
The step（1）Middle solvent is toluene, in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran It is one or more.
The present invention technique effect be：（1）Adsorbent of the present invention is compound with property of modified rectorite and modified meerschaum progress As basic adsorbent material, wherein, rectorite and sepiolite on its surface introduce organic group, extreme enrichment after being modified Its surface nature, improves its absorption property；And rectorite and sepiolite are used in combination, and play respective strong point, collaboration Effect, the alternative absorption variety classes organic and inorganic pollution different with molecular size also substantially increase its adsorptivity Can, greatly expand its application range；In addition, the present invention tires out support using four poly- surfactant of quaternary ammonium salt and chitosan to modified Stone and modified meerschaum compound carry out secondary cross-linking modification so that composite surface further inlays very big organic of molecular weight Group improves it and replaces performance and absorption property, improves its stability and intensity, and gained adsorbent is enable to stablize and efficiently Petrochemical wastewater is removed in absorption.
（2）It, can be fabulous using this method using the method for hydro-thermal reaction when adsorbent of the present invention carries out twice-modified The active group of modifying agent is anchored on property of modified rectorite and modified meerschaum compound, and sufficiently stable.
（3）Adsorbent of the present invention is due to having magnetism, and after absorption, the adsorbent can be under 20 minutes interior magnetic fields Thoroughly recycling, without filtering, settling, the extra process such as centrifuging.
Specific embodiment
Technical scheme of the present invention is further elaborated with reference to embodiment：
Embodiment 1
A kind of preparation method of petrochemical wastewater processing adsorbent, includes the following steps：
（1）The preparation of composite granule gel：Take 15 part of ten alkyl trimethyl phosphonium bromide property of modified rectorite powder and 20 part four Five amine modified meerschaum powder of ethylene is scattered in 100 parts of toluene, and ultrasonic vibration 1h at room temperature, then heats to 65 DEG C, 20 parts of ethyl orthosilicate is slowly added dropwise, continues stirring to solution and becomes solid phase；It is washed with distilled water and is solid to quality not Become, it is 3 hours dry at 100 DEG C, obtain composite granule gel；
（2）The preparation of modified compound adsorbent：By step（1）Obtained modified composite powder body gel is added to 10 parts of season It is mixed evenly in four poly- surfactant of ammonium salt, 6 parts of chitosan and 50 parts of toluene solvants, then shifts mixture Into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle at 80 DEG C hydro-thermal reaction 6h, reaction terminate centrifuged, washed, dry to get to Modified compound adsorbent；
（3）The preparation of magnetic coupling crosslinking adsorbent：By step（2）The modification compound adsorbent of acquisition is added to 30 parts In mixed molysite solution, in N2Under protection, 1 part a concentration of 28% of ammonium hydroxide is slowly added dropwise during stirring, in 40 DEG C of conditions Under be stirred to react 20 min and obtain the petrochemical wastewater processing adsorbent.
Embodiment 2
A kind of preparation method of petrochemical wastewater processing adsorbent, includes the following steps：
（1）The preparation of composite granule gel：Take 30 part of ten alkyl trimethyl phosphorus chloride property of modified rectorite powder and 20-40 parts Triethylene tetramine modified meerschaum powder is scattered in 180 parts of n,N-Dimethylformamide, and ultrasonic vibration 2h at room temperature, 75 DEG C are then heated to, 30 parts of ethyl orthosilicate is slowly added dropwise, continues stirring to solution and becomes solid phase；It is washed with distilled water solid It is 3 hours dry at 110 DEG C mutually to mass conservation, obtain composite granule gel；
（2）The preparation of modified compound adsorbent：By step（1）Obtained modified composite powder body gel is added to 15 parts of season It is mixed evenly in four poly- surfactant of ammonium salt, 12 parts of chitosan and 80 parts of toluene solvants, then turns mixture The hydro-thermal reaction 10h at 120 DEG C is moved on in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, reaction terminates centrifuged, washed, dried, i.e., Obtain modified compound adsorbent；
（3）The preparation of magnetic coupling crosslinking adsorbent：By step（2）The modification compound adsorbent of acquisition is added to 40 parts In mixed molysite solution, in N2Under protection, 2 parts a concentration of 28% of ammonium hydroxide is slowly added dropwise during stirring, in 40 DEG C of conditions Under be stirred to react 27 min and obtain the petrochemical wastewater processing adsorbent.
Embodiment 3
A kind of preparation method of petrochemical wastewater processing adsorbent, includes the following steps：
（1）The preparation of composite granule gel：Take 20 parts of cetyl triphenylphosphonium chloride property of modified rectorite powders and 30 parts Ethylenediamine modified meerschaum powder is scattered in 140 parts of n,N-dimethylacetamide, and ultrasonic vibration 1.5h at room temperature, so After be warming up to 70 DEG C, 25 parts of ethyl orthosilicate is slowly added dropwise, continues stirring and becomes solid phase to solution；It is washed with distilled water solid phase It is 5 hours dry at 105 DEG C to mass conservation, obtain composite granule gel；
（2）The preparation of modified compound adsorbent：By step（1）Obtained modified composite powder body gel is added to 12 parts of season It is mixed evenly in four poly- surfactant of ammonium salt, 9 parts of chitosan and 70 parts of toluene solvants, then shifts mixture Into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle at 100 DEG C hydro-thermal reaction 8h, reaction terminate centrifuged, washed, dry to get to Modified compound adsorbent；
（3）The preparation of magnetic coupling crosslinking adsorbent：By step（2）The modification compound adsorbent of acquisition is added to 35 parts In mixed molysite solution, in N2Under protection, 1.5 parts a concentration of 28% of ammonium hydroxide is slowly added dropwise during stirring, in 40 DEG C of items 25 min are stirred to react under part and obtain the petrochemical wastewater processing adsorbent.
Embodiment 4
A kind of preparation method of petrochemical wastewater processing adsorbent, includes the following steps：
（1）The preparation of composite granule gel：Take 25 part of ten alkyl trimethyl phosphonium bromide property of modified rectorite powder and 35 parts of second Ethylenediamine tetraacetic acid (EDTA) modified meerschaum powder is scattered in 160 parts of tetrahydrofuran, and ultrasonic vibration 1.8h at room temperature, Ran Housheng 28 parts of ethyl orthosilicate is slowly added dropwise to 70 DEG C in temperature, continues stirring to solution and becomes solid phase；It is washed with distilled water and is solid to matter Measure it is constant, it is 5 hours dry at 110 DEG C, obtain composite granule gel；
（2）The preparation of modified compound adsorbent：By step（1）Obtained modified composite powder body gel is added to 14 parts of season It is mixed evenly in four poly- surfactant of ammonium salt, 10 parts of chitosan and 70 parts of toluene solvants, then turns mixture Move on in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle the hydro-thermal reaction 9h at 110 DEG C, reaction terminates to be centrifuged, washed, dry to get To modified compound adsorbent；
（3）The preparation of magnetic coupling crosslinking adsorbent：By step（2）The modification compound adsorbent of acquisition is added to 38 parts In mixed molysite solution, in N2Under protection, 1.5 parts a concentration of 28% of ammonium hydroxide is slowly added dropwise during stirring, in 40 DEG C of items 25 min are stirred to react under part and obtain the petrochemical wastewater processing adsorbent.
Embodiment 5
A kind of preparation method of petrochemical wastewater processing adsorbent, includes the following steps：
（1）The preparation of composite granule gel：Take 18 part of ten alkyl trimethyl phosphorus chloride property of modified rectorite powder and 25 parts of second Ethylenediamine tetraacetic acid (EDTA) modified meerschaum powder is scattered in 130 parts of n,N-dimethylacetamide, and ultrasonic vibration 1h at room temperature, 75 DEG C are then heated to, 25 parts of ethyl orthosilicate is slowly added dropwise, continues stirring to solution and becomes solid phase；It is washed with distilled water solid It is 4 hours dry at 105 DEG C mutually to mass conservation, obtain composite granule gel；
（2）The preparation of modified compound adsorbent：By step（1）Obtained modified composite powder body gel is added to 12 parts of season It is mixed evenly in four poly- surfactant of ammonium salt, 9 parts of chitosan and 60 parts of toluene solvants, then shifts mixture Into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle at 90 DEG C hydro-thermal reaction 10h, reaction terminate centrifuged, washed, dry to get to Modified compound adsorbent；
（3）The preparation of magnetic coupling crosslinking adsorbent：By step（2）The modification compound adsorbent of acquisition is added to 33 parts In mixed molysite solution, in N2Under protection, 1.5 parts a concentration of 28% of ammonium hydroxide is slowly added dropwise during stirring, in 40 DEG C of items 22 min are stirred to react under part and obtain the petrochemical wastewater processing adsorbent.
Comparative example 1
Preparation method is same as Example 1, and uniquely difference lies in raw materials to use single sepiolite.
Comparative example 2
Preparation method is same as Example 1, and uniquely difference lies in steps（2）Middle modified feedstock is only with four poly- table of quaternary ammonium salt Face activating agent.
Comparative example 3
Preparation method is same as Example 1, and uniquely difference lies in steps（2）Hydro-thermal reaction be changed to normal pressure water-bath.
Adsorption experiment I：Embodiment 1-5 and comparative example 1-3 is to simulating the absorption containing waste water.
Simulated oily wastewater is handled using the absorbent particles after activation, simulation oil-containing water sample major parameter is as follows：COD is dense It spends for 1500.OmgL-1, oil concentration 982.0mgL-1, water sampling 40mL.
The dosage and adsorption conditions of adsorbent include：The dosage of absorbent particles is 25g/L, through counting 1g adsorbents, absorption Temperature is 40 DEG C, and adsorption time 120min, experimental result is shown in the following table 1.
It can be obtained by table 1, the adsorbent of embodiment 1-5 all shows good suction to COD in petrochemical wastewater and oil Attached performance, and the adsorbent better than comparative example 1-3.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used To modify to the technical solution recorded in foregoing embodiments or carry out equivalent replacement to which part technical characteristic. All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's Within protection domain.

Claims (5)

1. a kind of preparation method of petrochemical wastewater processing adsorbent, which is characterized in that include the following steps：
（1）The preparation of composite granule gel：Take the modified meerschaum powder point of 15-30 parts of property of modified rectorite powders and 20-40 parts It dissipates in 100-180 parts of solvent, and ultrasonic vibration 1-2h at room temperature, then heats to 65-75 DEG C, 20-30 is slowly added dropwise The ethyl orthosilicate of part continues stirring to solution and becomes solid phase；It is washed with distilled water and is solid to mass conservation, at 100-110 DEG C It is 3-6 hours dry, obtain composite granule gel；Wherein, modifying agent used in the property of modified rectorite powder is selected from ten alkane One kind in base trimethyl phosphonium bromide, ten alkyl trimethyl phosphorus chloride and cetyl triphenylphosphonium chloride；The modified sea Modifying agent used in afrodite powder is one in tetraethylenepentamine, triethylene tetramine, ethylenediamine or ethylenediamine tetra-acetic acid Kind；
（2）The preparation of modified compound adsorbent：By step（1）Obtained composite granule gel is added to 10-15 parts of quaternary ammonium salt It is mixed evenly in four poly- surfactants, 6-12 parts of chitosan and 50-80 parts of toluene solvants, then turns mixture The hydro-thermal reaction 6-10h at 80-120 DEG C is moved on in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, reaction terminates centrifuged, washed, dried It is dry to get to modified compound adsorbent；
（3）The preparation of magnetic composite adsorbent：By step（2）The modification compound adsorbent of acquisition is added to 30-40 parts of mixing In iron salt solutions, 1-2 parts a concentration of 28% of ammonium hydroxide is slowly added dropwise during stirring later, in N2Under protection, in 40 DEG C of items 20-30 min are stirred to react under part and obtain the petrochemical wastewater processing adsorbent.
2. preparation method according to claim 1, which is characterized in that the step（2）Middle four poly- surface-active of quaternary ammonium salt The preparation method of agent is：In the 250mL three-necked flasks equipped with condenser pipe, absolute ethyl alcohol 40mL, ethylenediamine 4.5g, room temperature are added in Magnetic agitation is carried out, epoxychloropropane 34.7g is added in 10 drops/min, 50 DEG C of back flow reaction 4h after being added dropwise, vacuum distillation After obtain four poly- surfactant-intermediates, be faint yellow translucent thick liquid, take intermediate 20g, adding in volume ratio is 1:The absolute ethyl alcohol and deionized water mixed solution 40mL of l is solvent, then 7.9gN is added dropwise, N- dimethyl dodecyl base tertiary amines, is risen Temperature reacts 1h to 80 DEG C, is evaporated under reduced pressure, and recrystallization, it is four poly- surface of quaternary ammonium salt that vacuum drying, which obtains white powdery solids, Activating agent.
3. preparation method according to claim 1, which is characterized in that the mixed molysite is that molar ratio is 1:1.5- 2.5 FeSO4·7H2O and FeC13·6H2The mixture of O.
4. preparation method according to claim 1, which is characterized in that the step（1）Middle solvent is toluene, N, N- diformazans It is one or more in base formamide, DMAC N,N' dimethyl acetamide, tetrahydrofuran.
5. the adsorbent that a kind of any one of claim 1-4 the methods are prepared.
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