CN110102249B - Preparation and regeneration method of adsorbent for adsorbing organic matters in oil refining wastewater - Google Patents
Preparation and regeneration method of adsorbent for adsorbing organic matters in oil refining wastewater Download PDFInfo
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- 238000011069 regeneration method Methods 0.000 title claims abstract description 77
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- 238000007670 refining Methods 0.000 title abstract description 21
- 239000002351 wastewater Substances 0.000 title description 4
- 230000008929 regeneration Effects 0.000 claims abstract description 69
- 239000002699 waste material Substances 0.000 claims abstract description 66
- 239000010865 sewage Substances 0.000 claims abstract description 61
- 238000001179 sorption measurement Methods 0.000 claims abstract description 53
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- 239000003513 alkali Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
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- 239000012466 permeate Substances 0.000 claims description 16
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- 238000006243 chemical reaction Methods 0.000 claims description 8
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- 229910003112 MgO-Al2O3 Inorganic materials 0.000 abstract description 10
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- 230000008021 deposition Effects 0.000 description 7
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 206010003549 asthenia Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention discloses a preparation method of an adsorbent for adsorbing organic matters in oil refining sewage, wherein the adsorbent is waste Co-Mo/MgO-Al subjected to treatment and modification2O3The sulfur-resistant shift catalyst is subjected to organic acid pretreatment after primary roasting; adding mixed solution of Na, K and F soluble salts, organic alkali and alcohols, and carrying out hydrothermal treatment; after secondary roasting, the obtained product is used as an adsorbent for organic matters in the oil refining sewage. The adsorbent is not only waste Co-Mo/MgO-Al2O3The sulfur tolerant shift catalyst provides a new utilization method, and has the characteristics of good organic matter adsorption capacity in oil refining sewage, good regeneration performance in high-concentration alkaline solution and difficult pulverization.
Description
Technical Field
The invention relates to the field of oil refining sewage treatment, in particular to a preparation and regeneration method of an adsorbent for adsorbing organic matters in oil refining sewage.
Background
At present, after sewage of many oil refining enterprises is treated, Chemical Oxygen Demand (COD) still exceeds standard and is inferior sewage. If the system is recycled, certain harm can be caused to the system operation; if the waste water is directly discharged, the environment pollution is caused. Therefore, the inferior sewage needs to be further treated, and the organic waste in the inferior sewage is effectively reduced so as to be recycled or directly discharged.
The adsorption method is one of the sewage treatment methods, and the selection of a proper adsorbent is the key of the adsorption technology. The currently commonly used adsorbents comprise active carbon, humic acids, resins and the like, and the synthesis and regeneration cost of the adsorbents is high, so that the application of the adsorbents is limited to a certain extent. The waste catalyst has the characteristics of high specific surface area, developed pore structure, rich sources and the like, realizes the reutilization of solid wastes, and can greatly reduce the cost of sewage treatment.
In the coal chemical industry and petrochemical industry, the shift reaction for preparing hydrogen and carbon dioxide from carbon monoxide and water vapor is widely used for preparing hydrogen and carbon dioxideTaking ammonia synthesis gas, hydrogen and oxo synthesis gas. In order to meet the requirement of preparing high-sulfur-content synthetic gas by using heavy oil, coal and vacuum residuum as raw materials in the sixties of the twentieth century, the invention provides a Co-Mo series sulfur-tolerant shift catalyst, wherein Co-Mo/MgO-Al is used2O3The catalyst has high hydrothermal stability and is widely applied. When the shift unit is used to replace catalyst, a large amount of solid waste is generated.
Literature (Zuli, Li Feng, Yuehong, Ma Xin, Li Ben Gao. research on adsorption performance of oil refining waste catalyst on organic matter in inferior sewage [ J)]Industrial water treatment, 2008(05), 54-56), organic matters in the inferior sewage are treated by using the waste oil refining catalyst as an adsorbent; patent CN1814556 discloses a method for treating sewage by using oil refining waste catalyst, wherein Al in the waste catalyst2O3The content of (A) is 45-70%, SiO2The content of (A) is 25-50%. However, such a catalyst is Al2O3Is the main component, and in the process of alkaline and hydrothermal regeneration, the Si-Al skeleton is damaged under the condition of high alkalinity, and is easy to pulverize, so that the strength is reduced.
In addition, the existing adsorbent is difficult to regenerate, or cannot realize automatic regeneration in the regeneration process, so that the adsorbent is not easy to be recycled for multiple times.
Disclosure of Invention
The invention provides a method for preparing a high-purity aluminum by utilizing waste Co-Mo/MgO-Al2O3A process for adsorbing the organic substances in sewage generated by oil refining by using sulfur-resistant transform catalyst as adsorbent.
Due to the waste Co-Mo/MgO-Al2O3Under the use atmosphere of high temperature and high water-gas ratio, active components of the sulfur-resistant shift catalyst are sintered and agglomerated to be larger, and the carrier structure is changed to a certain degree, so that the hydrothermal stability is greatly reduced; meanwhile, the superfine coal ash in the raw material gas is adsorbed, and carbon deposition can be generated in the reaction process, so that pore channels are blocked and blocked; in addition, the sulfur-tolerant shift catalyst is active in a sulfided state, so the waste shift catalyst is in a sulfided state and is easy to spontaneously combust in air.
In order to solve the problems, the technical scheme of the invention is as follows:
a preparation method of an adsorbent for adsorbing organic matters in oil refining sewage comprises the following steps:
1) carrying out primary roasting on the waste cobalt-molybdenum sulfur-tolerant shift catalyst;
2) pretreating the oxidized waste sulfur-tolerant shift catalyst after primary roasting;
3) transferring the pretreated waste catalyst into a reaction kettle, adding a treating agent consisting of Na, K and F soluble salts and a mixed solution of organic alkali and alcohols, and carrying out hydrothermal treatment;
4) after the treatment, filtering, washing and roasting for the second time to obtain the adsorbent; wherein,
in the step 1), the roasting temperature is 250-; in the step 4), the secondary roasting temperature is 450-650 ℃, and the treatment time is 2-8 h.
Preferably, in step 2), the solution for pretreatment is one or a mixture of more of citric acid, oxalic acid, tartaric acid and maleic acid, and the dosage is acid/(Co + Mo): 0.40-1.6 mol/mol.
Preferably, in the step 2), the pretreatment temperature is 20-80 ℃ and the treatment time is 2-24 h.
Preferably, in the step 3), the dosage of Na, K and F soluble salts in the treating agent is 5-10% of the mass of the catalyst.
Preferably, in the step 3), the organic base in the treating agent is one or more of TPAOH, TEAOH, TBAOH, betaine and urotropin, and the pH of the system is controlled to be 8-12.
Preferably, in step 3), the amount of alcohol in the treating agent is alcohol/organic base: 0.50-2.0 mol/mol.
Preferably, in the step 3), the temperature of the hydrothermal treatment is 85-110 ℃ and the treatment time is 2-24 h.
The adsorbent prepared by the preparation method is used for adsorbing organic matters in oil refining sewage.
The use and regeneration method of the adsorbent for adsorbing the organic matters in the refinery sewage comprises the following specific steps:
s1, filling the adsorbent into adsorption cylinders of the first-class and second-class reactors;
the S2 controller controls the first-class electric regulating valve to open, the second-class electric regulating valve to close, the first-class three-way electric regulating valve to close, the second-class three-way electric regulating valve to open to the regeneration alkali lye input port, the first-class four-way electric regulating valve to open to the sewage input port side, and the second-class four-way electric regulating valve to open to the regeneration waste lye discharge port side;
s3 sewage enters an input cylinder of a reactor, is shunted by an input branch line and enters a fan-shaped cylinder, is scattered by a spoiler in the process of entering the fan-shaped cylinder, permeates into an adsorption cylinder, filters an adsorbent filled in the adsorption cylinder, permeates into a central cylinder, flows out of the reactor through an output cylinder and flows out through a sewage output port;
in the process of sewage adsorption S4, if any one of the online differential pressure display device and the COD online monitor monitors that any one of the differential pressure value and the COD value reaches the upper limit threshold value, the controller controls the first-class electric regulating valve to be closed, the second-class electric regulating valve to be opened, the first-class three-way electric regulating valve is opened to a regenerated alkali liquor input port, the second-class three-way electric regulating valve is closed, the first-class four-way electric regulating valve is opened to a regenerated waste alkali liquor discharge port side, and the second-class four-way electric regulating valve is opened to a sewage output port side; the sewage enters a second-class reactor for adsorption treatment, the regenerated alkali liquor enters a quick-seepage device of the first-class reactor and permeates into an adsorption cylinder to regenerate the adsorbent, and the regenerated waste alkali liquor permeates into a central cylinder, flows out of the first-class reactor through an output cylinder and flows out through a regenerated waste alkali liquor outlet;
s5, in the process of adsorbent regeneration, if the COD on-line monitor monitors that the COD value is smaller than the lower limit threshold value, the controller controls one type of three-way electric regulating valve to open towards the regeneration acid liquor input port, and the one type of four-way electric regulating valve to open towards the regeneration waste acid liquor discharge port; the regenerated waste acid liquid enters the quick seepage device of the first-class reactor and seeps into the adsorption cylinder to neutralize the alkali remained in the adsorbent, and the regenerated waste acid liquid seeps into the central cylinder, flows out of the first-class reactor through the output cylinder and flows out of the regenerated waste acid liquid outlet; after the acid liquor for regeneration is input for a period of time, the three-way electric regulating valve is closed;
s6, when the regeneration of the adsorbent of the first type reactor is finished and the adsorbent of the second type reactor reaches the upper adsorption limit, repeating the steps and circulating in sequence.
Preferably, the regeneration acid solution input duration in the step S5 is 20-40 min.
According to the preparation method provided by the invention, after primary roasting, sulfur and carbon deposition are removed, acid pretreatment is carried out, active components are re-dispersed, the size of the active components is reduced, alumina fragments blocking pore channels are dissolved out, pore channel distribution is regulated and controlled, and a proper pore channel is created for adsorbing organic matters in oil refining sewage; hydrothermal treatment to free MgO and Al in the carrier2O3Performing interaction to generate a magnesium aluminate spinel precursor; after secondary roasting, the content of the magnesium aluminate spinel in the waste catalyst is greatly improved, and the hydrothermal stability when the catalyst is used as an adsorbent is enhanced.
To treat the modified waste Co-Mo/MgO-Al2O3The cobalt-molybdenum sulfur-tolerant shift catalyst is used as an adsorbent, breaks through the limitation that the existing waste oil refining catalyst is used as the adsorbent and is easy to be pulverized when being regenerated in high-concentration alkali liquor, and is waste Co-Mo/MgO-Al2O3The reuse of sulfur-tolerant shift catalyst provides a pioneering method, and the treated waste Co-Mo/MgO-Al2O3The cobalt-molybdenum sulfur-tolerant shift catalyst has greatly increased content of magnesium aluminate spinel structure, and especially has hydration heat resistance and chemical stability far higher than those of other waste oil refining catalysts; the pore channel structure is re-optimized, and the specific surface area is recovered, so that the adsorption capacity is increased. The adsorbent prepared by the preparation method provided by the invention has better COD removal performance in the aspect of sewage treatment.
In the regeneration method, the automatic regeneration is realized through the cooperation of the online differential pressure display device, the COD online monitor and the controller, so that the regeneration efficiency is improved, and the adsorption effect is ensured; in addition, the turbulent flow device is arranged in the reactor, so that sewage enters the adsorption cylinder from top to bottom, and the uniform adsorption of the adsorbent is ensured; the quick permeation of the regenerated alkali liquor and the regenerated acid liquor into the adsorbent is realized through the quick permeation device, and the quick regeneration of the adsorbent is realized.
The foregoing is a summary of the present disclosure, and for the purposes of promoting a clear understanding of the technical aspects of the present disclosure, and enabling the same to be implemented in accordance with the present disclosure, the following detailed description of the preferred embodiments of the present disclosure, along with the accompanying drawings, will be made in order to make the foregoing and other objects, features, and advantages of the present disclosure more comprehensible.
The above and other objects, advantages and features of the present application will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without inventive work. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a schematic view of an automatic adsorbent regenerating apparatus according to the present invention;
FIG. 2 is an external view of a reactor of the automatic adsorbent regenerating apparatus of the present invention;
FIG. 3 is a sectional view of the main structure of the reactor (without flow perturbation means and fast permeation means) of the automatic adsorbent regeneration device of the present invention;
FIG. 4 is a schematic view of a turbulent flow device and a fast permeation device of a reactor of an automatic adsorbent regeneration device according to the present invention;
FIG. 5 is a schematic view of a rapid-permeation device of an automatic adsorbent regeneration device according to the present invention;
FIG. 6 is a schematic view of a dynamic adsorption apparatus for performance test of the adsorbent according to the present invention;
wherein, 1-regeneration alkali liquor input port; 2-inputting an acid liquor for regeneration; 3-discharging regenerated waste lye; 4-regenerated spent acid liquor discharge port; 5-an online differential pressure display device; 6-electric regulating valve; 7-three-way electric control valve; 8-a controller; 9-a reactor; 10-COD on-line monitor; 11-a sewage input port; 12-a sewage outlet; 13-four-way electric control valve; 14-a housing; 15-a sector cylinder; 16-a central cylinder; 17-an input cylinder; 18-input branch; 19-an upper baffle plate; 20-a lower baffle; 21-a flow perturbation device; 22-a rapid infiltration device; 23-an output cartridge; 25-a regeneration liquid input pipeline; 32-adsorption cartridge.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. In the following description, specific details such as specific configurations and components are provided only to help the embodiments of the present application be fully understood. Accordingly, it will be apparent to those skilled in the art that various changes and modifications may be made to the embodiments described herein without departing from the scope and spirit of the present application. In addition, descriptions of well-known functions and constructions are omitted in the embodiments for the sake of clarity and conciseness.
It should be appreciated that reference throughout this specification to "one embodiment" or "the embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present application. Thus, the appearances of the phrase "one embodiment" or "the present embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
Further, the present application may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
It is further noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion.
Example 1
Waste Co-Mo/MgO-Al2O3Carrying out primary roasting on the sulfur-resistant shift catalyst under the roasting condition of 300 ℃ for 2h to remove carbon deposition and sulfur; soaking citric acid by an isometric soaking method, wherein the acid dosage is 0.50mol/mol of acid/(Co + Mo), and the acid treatment condition is 60 ℃ and 12 hours; loading into a reaction kettle, adding NaF accounting for 7% of the mass of the waste catalyst, adding tetrapropylammonium hydroxide (TPAOH) solution and deionized water, adjusting the pH to 10, adding propanol with the dosage of 1.10mol/mol of propanol/TPAOH, treating at 100 ℃ for 6h, cooling to room temperature, washing with deionized water, and drying at 110 ℃ for 6 h; and (4) carrying out secondary roasting, wherein the roasting condition is 450 ℃ and the roasting time is 4 hours, and screening to obtain the adsorbent A-1.
Example 2
Waste Co-Mo/MgO-Al2O3Carrying out primary roasting on the sulfur-resistant shift catalyst under the roasting condition of 250 ℃ for 4 hours to remove carbon deposition and sulfur; soaking citric acid by an isometric soaking method, wherein the acid dosage is 1.00mol/mol of acid/(Co + Mo), and the acid treatment condition is 50 ℃ and 17 hours; loading into a reaction kettle, and adding NH accounting for 9 percent of the mass of the waste catalyst4F, adding tetrabutylammonium hydroxide (TBAOH) solution and deionized water, adjusting the pH to 9, adding ethylene glycol with the dosage of 0.90mol/mol of ethylene glycol/TBAOH, treating at 90 ℃ for 8h, cooling to room temperature, washing with deionized water, and drying at 120 ℃ for 4 h; and (4) carrying out secondary roasting, wherein the roasting condition is 520 ℃, and the obtained adsorbent is marked as A-2 after screening.
Example 3
Waste Co-Mo/MgO-Al2O3Carrying out primary roasting on the sulfur-resistant shift catalyst under the roasting condition of 350 ℃ for 2.5 hours to remove carbon deposition and sulfur; soaking a mixture of citric acid and oxalic acid (the molar ratio of the citric acid to the oxalic acid is 1:1) by adopting an isometric soaking method, wherein the acid dosage is 0.80mol/mol of acid/(Co + Mo), and the acid treatment condition is 90 ℃ and 8 hours; loading into a reaction kettle, addingKF with the mass of 10% of the waste catalyst is added, betaine solution and deionized water are added, the pH is adjusted to 10.5, butanol is added, the amount of the butanol/the betaine is 1.40mol/mol, the mixture is treated at 110 ℃ for 4 hours, cooled to room temperature, washed by the deionized water, and dried at 120 ℃ for 3 hours; and (3) carrying out secondary roasting, wherein the roasting condition is 500 ℃, and the obtained adsorbent is marked as A-3 after screening is carried out.
Example 4
Waste Co-Mo/MgO-Al2O3Carrying out primary roasting on the sulfur-resistant shift catalyst under the roasting condition of 350 ℃ for 2.5 hours to remove carbon deposition and sulfur; soaking tartaric acid by an isometric soaking method, wherein the dosage of the acid is 1.20mol/mol of acid/(Co + Mo), and the acid treatment condition is 80 ℃ and 12 hours; loading into a reaction kettle, and adding Na accounting for 12 percent of the mass of the waste catalyst2CO3Adding tetraethyl ammonium hydroxide (TEAOH) solution and deionized water, adjusting the pH to 9.5, adding mixed alcohol of ethanol and propanol (the molar ratio is 1:1) with the use amount of total alcohol/TEAOH being 0.80mol/mol, treating at 85 ℃ for 8h, cooling to room temperature, washing with deionized water, and drying at 120 ℃ for 6 h; and (3) carrying out secondary roasting under the roasting condition of 550 ℃ for 1.5h, and screening to obtain the adsorbent A-4.
Example 5
In addition to the above embodiments, an automatic regeneration and use method capable of automatically regenerating the adsorbent is further provided.
The regeneration method is based on an automatic regeneration device, and the automatic regeneration device comprises a sewage inlet 11, a regeneration alkali liquor inlet 1, a regeneration acid liquor inlet 2, at least two reactors 9, a regeneration waste alkali liquor outlet 3, a regeneration waste acid liquor outlet 4, a sewage outlet 12 and a controller 8, and is shown in figure 1.
The reactor 9 comprises an input drum, a regeneration liquid input pipeline and an output drum.
The input cylinder of each reactor 9 is respectively connected with one end of an electric regulating valve 6, and the other end of the electric regulating valve 6 is connected with the sewage input port 11.
The regeneration liquid input pipeline of each reactor 9 is respectively connected with one end of a three-way electric control valve 7, and the other two ends of the three-way electric control valve 7 are respectively connected with the regeneration alkali liquid input port 1 and the regeneration acid liquid input port 2.
The output cylinder of each reactor 9 is respectively connected with one end of a four-way electric regulating valve 13, and the other three ends of the four-way electric regulating valve 13 are respectively connected with a regenerated waste alkali liquor outlet 3, a regenerated waste acid liquor outlet 4 and a sewage outlet 12.
The electric regulating valves 6, the three-way electric regulating valve 7 and the four-way electric regulating valve 13 are the same as the reactors 9 in number and are in one-to-one correspondence.
Each reactor 9 is connected with an online differential pressure display device 5, and the online differential pressure display devices 5 are used for monitoring the differential pressure between the inlet and the outlet of the reactor.
Each four-way electric control valve 13 is provided with a COD on-line monitor 10, and the COD of the sewage after adsorption is monitored by the COD on-line monitor 10.
The controller 8 is respectively connected to each electric control valve 6, the three-way electric control valve 7, the four-way electric control valve 13, the online differential pressure display device 5 and the COD online monitor 10.
As a preference, with reference to fig. 1, the number of reactors 9 is 4.
The reactor 9 is divided into a first-class reactor and a second-class reactor, and the electric control valve 6, the three-way electric control valve 7, the online differential pressure display device 5, the COD online monitor 10 and the four-way electric control valve 13 which correspond to the reactors are also divided into a first-class electric control valve and a second-class electric control valve, a first-class three-way electric control valve and a second-class three-way electric control valve, a first-class online differential pressure display device and a second-class online differential pressure display device, a first-class COD online monitor and a second-class COD online monitor, a first-class four-way electric control valve and a second-class four-way electric control valve.
Preferably, the reactor 9 further comprises a reactor main body, a liquid separation device, a flow disturbing device 21 and a fast permeation device 22.
The reactor main body comprises a shell 14, an upper baffle plate 19 and a lower baffle plate 20 are respectively horizontally arranged at the upper part and the lower part in the shell 14, and an adsorption regeneration space is formed between the upper baffle plate 19 and the lower baffle plate 20. A central cylinder 16 is arranged at the central position of the adsorption regeneration space; the upper end of the central cylinder 16 is connected with an upper baffle plate 19, and the lower end of the central cylinder extends to the outer side of the shell 14 to form an output cylinder 23, wherein the output cylinder 23 is a liquid output pipeline of the reactor 9; holes are uniformly distributed on the wall of the central cylinder 16. The position that is close to shell 14 in the absorption regeneration space is provided with a plurality of arcs, every form fan-shaped section of thick bamboo 15 between arc all and the shell 14, the equipartition is porose on the arc, the aperture of hole is less than on the arc the diameter of adsorbent to avoid the adsorbent to leak into in the fan-shaped section of thick bamboo 15. An adsorption cylinder 32 is formed between the sector cylinder 15 and the central cylinder 16, and the adsorbent is filled in the adsorption cylinder 32.
The liquid separating device is arranged at the top of the reactor main body and comprises an input cylinder 17 and an input branch line 18. Wherein the input cylinder 17 is a sewage input pipeline of the reactor 9. One end of the input cylinder 17 penetrates through the top of the shell 14 and is connected with the sewage input port 11 through the electric regulating valve 6, and the other end of the input cylinder is a plugging end. The blocking end is positioned at the upper part of the upper baffle plate 19, the side edge of the bottom of the blocking end is communicated with the input branch lines 18, the number of the input branch lines 18 is equal to that of the fan-shaped cylinders 15, and each input branch line 18 is communicated with the fan-shaped cylinder 15 through the upper baffle plate 19.
The utility model discloses a fan-shaped section of thick bamboo, including a fan-shaped section of thick bamboo 15, spoiler device 21 set up in the fan-shaped section of thick bamboo 15, every all be provided with spoiler device 21 in the fan-shaped section of thick bamboo 15, spoiler device 21 includes the stand, the stand bottom is fixed on baffle 20 down, stand upper portion is fixed in the inner wall of fan-shaped section of thick bamboo 15 through the support vertically evenly is provided with a plurality of spoilers on the stand, the spoilers all are mutually perpendicular with the stand, and a plurality of spoilers are all different from each other to set up the angle. The flow disturbing device 21 can prevent sewage from directly falling to the bottom of the fan-shaped cylinder 15 when entering the fan-shaped cylinder 15. If there is not the vortex device, sewage directly falls to the bottom of fan-shaped section of thick bamboo 15, can lead to the adsorbent of only bottom to handle sewage for the adsorbent of bottom has the throughput saturation, and the adsorbent on upper portion still has the adsorption potential, causes the imbalance of adsorbent adsorption efficiency. The sewage is beaten into the adsorption cylinder 32 by the spoiler in the process of descending again through the spoiler 21, so that the upper adsorbent can adsorb as much sewage as possible.
The fast-permeation device 22 is formed by surrounding a fast-permeation tube around the central cylinder 16 from the upper baffle plate 19 to the lower baffle plate 20. The top of the fast permeation pipe is communicated with a regenerated liquid input pipeline 25 through an upper baffle plate 19, and the tail end of the fast permeation pipe is blocked. The last equipartition of rapid infiltration pipe has the pore, the aperture of pore is less than the size of adsorbent to avoid the adsorbent to get into in the rapid infiltration pipe.
The automatic regeneration and use method capable of automatically regenerating the adsorbent specifically comprises the following steps:
(1) filling the adsorbent into the adsorption cartridges 32 of the first-type and second-type reactors;
(2) the controller 8 controls the first-class electric regulating valve to be opened, the second-class electric regulating valve to be closed, the first-class three-way electric regulating valve to be closed, the second-class three-way electric regulating valve to be opened to the regenerated alkali liquor inlet 1, the first-class four-way electric regulating valve to be opened to the sewage outlet 12 side, and the second-class four-way electric regulating valve to be opened to the regenerated waste alkali liquor outlet 3 side;
(3) sewage enters an input cylinder 17 of a reactor from a sewage input port 11, is further divided by an input branch line 18 and enters a fan-shaped cylinder 15, is scattered by a flow disturbing plate in the descending process after entering the fan-shaped cylinder, permeates into an adsorption cylinder 32 through holes in the fan-shaped cylinder 15 and is further filtered by an adsorbent filled in the adsorption cylinder 32, and the filtered sewage permeates into a central cylinder 16 through holes in the central cylinder 16, then flows out of the reactor 9 through an output cylinder 23 and further flows out through a sewage output port 12;
(4) in the process of sewage adsorption, the online differential pressure display device 5 and the COD online monitor 10 continuously monitor the pressure difference value between the inlet and the outlet of the first type of reactor and the COD value of the adsorbed sewage, the online differential pressure display device 5 and the COD online monitor 10 are respectively provided with an upper limit threshold value of the pressure difference value and the COD value, if any one of the pressure difference value and the COD value reaches the upper limit threshold value, the adsorbent in the reactor is indicated to reach the adsorption upper limit, at the moment, the controller 8 controls the first type of electric regulating valve to be closed, the second type of electric regulating valve to be opened, the first type of three-way electric regulating valve is opened to the regeneration alkaline liquor inlet 1, the second type of three-way electric regulating valve is closed, the first type of four-way electric regulating valve is opened to the regeneration waste alkaline liquor outlet 3 side, and the second type of four-way electric regulating valve is opened to the sewage outlet 12 side; at the moment, sewage enters a second-class reactor for adsorption treatment, alkali liquor for regeneration enters a quick-permeation device 22 of the first-class reactor from a regeneration alkali liquor inlet 1, and permeates into an adsorption cylinder 32 through pores on the quick-permeation device 22 to regenerate the adsorbent, and regenerated waste alkali liquor permeates into a central cylinder 16 through pores on the central cylinder 16, then flows out of the first-class reactor through an output cylinder 23, and then flows out through a regeneration waste alkali liquor outlet 3;
(5) in the regeneration process of the adsorbent, the COD online monitor 10 continuously monitors the COD value in the regenerated waste alkali liquor, the COD online monitor 10 is provided with a lower limit threshold value of the COD value, and if the monitored COD value is smaller than the lower limit threshold value, the regeneration of the adsorbent in the reactor is finished. At this time, the controller 8 controls the first-class three-way electric regulating valve to open towards the regeneration acid liquid inlet 2, and the first-class four-way electric regulating valve to open towards the regeneration waste acid liquid outlet 4; at the moment, the regeneration acid liquor enters the quick-permeation device 22 of the first-class reactor from the regeneration acid liquor inlet 2, and permeates into the adsorption cylinder 32 through the pores on the quick-permeation device 22 to neutralize the alkali liquor remained in the adsorbent, and the regenerated waste acid liquor permeates into the central cylinder 16 through the pores on the central cylinder 16, then flows out of the first-class reactor through the output cylinder 23 and flows out through the regeneration waste acid liquor outlet 4; after the regenerated acid liquid is input for a period of time, the three-way electric regulating valve is closed;
preferably, the input time of the acid solution for regeneration lasts 20-40 min;
it should be noted that if the first type of reactor has been regenerated and the second type of reactor has not been completely adsorbed, the controller 8 can control the first type of electric control valve to remain closed, the first type of three-way electric control valve to be closed, and the first type of four-way electric control valve to be opened toward the sewage outlet 12.
(6) And (3) when the regeneration of the adsorbent of the first-class reactor is finished and the adsorbent of the second-class reactor reaches the upper adsorption limit, repeating the step (2) and circulating in sequence.
Performance testing
The dynamic adsorption device is shown in figure 6, wherein the diameter of the glass column is 38mm, the flow rate of the oil refining wastewater is 37mm/h, the filling height of the adsorbent is 5mm, the diameter of the crushed adsorbent is 0.1mm, and the work period is 60.75 h. Wherein, COD of the feeding and the discharging is measured by a COD rapid measuring instrument (CTL-12).
Study of adsorbent regeneration Performance 100mL of regeneration solution (10 wt% NaHCO) was added to each 250mL conical flask3Solution) and a certain amount of adsorbent saturated by the oil refining sewage, shaking for a certain time, pouring the regeneration liquid, filtering the adsorbent, and drying for later use. Accurately weighing about 1g of regenerated adsorbent, adding 100mL of refinery sewage, oscillating for 20h, measuring COD of the solution after adsorption balance, and simultaneously carrying out adsorption test of the adsorbent with the same mass.
The strength of the adsorbent before and after regeneration is measured by a DLIII intelligent particle strength tester, and the influence of alkali liquor regeneration on the crushing strength of the catalyst is inspected.
Comparative example 1
Taking waste Co-Mo/MgO-Al discharged from an industrial reactor2O3And (3) carrying out primary roasting on the sulfur-resistant shift catalyst under the roasting condition of 300 ℃ for 2h, removing carbon deposition and sulfur, and screening to obtain adsorption A-0.
TABLE 1 adsorption Performance of different adsorbents
TABLE 2 regeneration efficiency of different adsorbents in alkaline solution
TABLE 3 strength change after regeneration of different adsorbents in alkaline solution
From the adsorption performance of different adsorbents, the COD removal rate of the waste sulfur-tolerant shift catalyst adsorbent prepared by the method provided by the invention is more than 76%, while the untreated waste sulfur-tolerant shift catalyst is only about 30%, which shows that the method provided by the invention has the advantages of dredging the pore channel of the catalyst, improving the pore channel structure and being more beneficial to the adsorption of COD; the dynamic adsorption capacity is more than 40mg/g, which is superior to 34.21mg/g of the dynamic adsorption capacity of the waste oil refining catalyst reported in the literature (Zhangli, Lifeng, Yuehong, Maxin, high plum., research on the adsorption performance of the waste oil refining catalyst on organic matters in inferior sewage [ J ] industrial water treatment, 2008(05): 54-56.).
The waste Co-Mo/MgO-Al treated by the method is analyzed from the change conditions of the regeneration performance and the strength of the adsorbent under the condition of high-concentration alkali liquor2O3The strength retention degree of the regenerated sulfur-tolerant shift catalyst is more than 98 percent, the strength loss is small, the pulverization is not easy, and the regeneration performance is good; the strength loss of the waste and old which is not treated by the method of the invention is more than 20 percent, and the strength stability is poorer.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof. All changes in structure made without creative work from the conception of the invention fall into the protection scope of the invention.
Claims (2)
1. A method for using and regenerating an adsorbent for adsorbing organic matters in refinery sewage is characterized in that the adsorbent is prepared by the following preparation method:
1) carrying out primary roasting on the waste cobalt-molybdenum sulfur-tolerant shift catalyst;
2) pretreating the oxidized waste sulfur-tolerant shift catalyst after primary roasting;
3) transferring the pretreated waste catalyst into a reaction kettle, adding a treating agent consisting of Na, K and F soluble salts and a mixed solution of organic alkali and alcohols, and carrying out hydrothermal treatment;
4) after the treatment, filtering, washing and roasting for the second time to obtain the adsorbent; wherein,
in the step 1), the roasting temperature is 250-; in the step 2), the solution for pretreatment is one or a mixture of more of citric acid, oxalic acid, tartaric acid and maleic acid, and the dosage is acid/(Co + Mo): 0.40-1.6 mol/mol; in the step 2), the pretreatment temperature is 20-80 ℃, and the treatment time is 2-24 h; in the step 3), the dosage of Na, K and F soluble salts in the treating agent is 5-10% of the mass of the catalyst; in the step 3), the organic alkali in the treating agent is one or more of TPAOH, TEAOH, TBAOH, betaine and urotropine, and the pH of the system is controlled to be 8-12; in the step 3), the alcohol dosage in the treating agent is alcohol/organic alkali: 0.50-2.0 mol/mol; in the step 3), the temperature of the hydrothermal treatment is 85-110 ℃, and the treatment time is 2-24 h; in the step 4), the secondary roasting temperature is 450-;
the method for using and regenerating the adsorbent comprises the following specific steps:
s1, filling the adsorbent into adsorption cylinders of the first-class and second-class reactors;
the S2 controller controls the first-class electric regulating valve to open, the second-class electric regulating valve to close, the first-class three-way electric regulating valve to close, the second-class three-way electric regulating valve to open to the regeneration alkali lye input port, the first-class four-way electric regulating valve to open to the sewage output port, and the second-class four-way electric regulating valve to open to the regeneration waste lye discharge port;
s3 sewage enters an input cylinder of a reactor, is shunted by an input branch line to enter a fan-shaped cylinder, is scattered by a spoiler in the process of entering the fan-shaped cylinder, permeates into an adsorption cylinder, filters an adsorbent filled in the adsorption cylinder, permeates into a central cylinder, flows out of the reactor through an output cylinder and flows out through a sewage output port;
in the process of sewage adsorption S4, if any one of the online differential pressure display device and the COD online monitor monitors that any one of the differential pressure value and the COD value reaches the upper limit threshold value, the controller controls the first-class electric regulating valve to be closed, the second-class electric regulating valve to be opened, the first-class three-way electric regulating valve is opened to a regeneration alkali liquor input port, the second-class three-way electric regulating valve is closed, the first-class four-way electric regulating valve is opened to a regeneration waste alkali liquor discharge port side, and the second-class four-way electric regulating valve is opened to a sewage output port side; the sewage enters a second-class reactor for adsorption treatment, the regenerated alkali liquor enters a quick-seepage device of the first-class reactor and permeates into an adsorption cylinder to regenerate the adsorbent, and the regenerated waste alkali liquor permeates into a central cylinder, flows out of the first-class reactor through an output cylinder and flows out through a regenerated waste alkali liquor outlet;
s5, in the process of adsorbent regeneration, if the COD on-line monitor monitors that the COD value is smaller than the lower limit threshold value, the controller controls one type of three-way electric regulating valve to open towards the regeneration acid liquor input port, and the one type of four-way electric regulating valve to open towards the regeneration waste acid liquor discharge port; the regenerated waste acid liquid enters a quick-seepage device of the first-class reactor and permeates into the adsorption cylinder to neutralize the alkali remained in the adsorbent, and the regenerated waste acid liquid permeates into the central cylinder, flows out of the first-class reactor through the output cylinder and flows out through a regenerated waste acid liquid outlet; after the acid liquor for regeneration is input for a period of time, the three-way electric regulating valve is closed;
s6, when the regeneration of the adsorbent of the first type reactor is finished and the adsorbent of the second type reactor reaches the upper adsorption limit, repeating the steps and circulating in sequence.
2. The use and regeneration method of claim 1, wherein the regeneration acid liquid input duration in step S5 is 20-40 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101801853A (en) * | 2007-09-21 | 2010-08-11 | 浦项产业科学研究院 | Method of manufacturing Fe and Ni containing material and cobalt containing material using recycling residue of spent catalyst and method of manufacturing raw material for stainless using the Fe and Ni containing material and method of manufacturing Fe-Ni alloy |
| WO2012009516A2 (en) * | 2010-07-15 | 2012-01-19 | Exxonmobil Research And Engineering Company | Hydroprocessing of biocomponent feeds with low pressure hydrogen-containing streams |
| CN103553104A (en) * | 2013-09-29 | 2014-02-05 | 大连瑞克科技有限公司 | Recovery method for waste CO sulfur tolerant shift catalyst |
| CN108043418A (en) * | 2017-11-24 | 2018-05-18 | 湖北双雄催化剂有限公司 | A kind of preparation method of low cost high stability sulfur-resistant transformation catalyst |
-
2019
- 2019-05-10 CN CN201910370972.2A patent/CN110102249B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101801853A (en) * | 2007-09-21 | 2010-08-11 | 浦项产业科学研究院 | Method of manufacturing Fe and Ni containing material and cobalt containing material using recycling residue of spent catalyst and method of manufacturing raw material for stainless using the Fe and Ni containing material and method of manufacturing Fe-Ni alloy |
| WO2012009516A2 (en) * | 2010-07-15 | 2012-01-19 | Exxonmobil Research And Engineering Company | Hydroprocessing of biocomponent feeds with low pressure hydrogen-containing streams |
| CN103553104A (en) * | 2013-09-29 | 2014-02-05 | 大连瑞克科技有限公司 | Recovery method for waste CO sulfur tolerant shift catalyst |
| CN108043418A (en) * | 2017-11-24 | 2018-05-18 | 湖北双雄催化剂有限公司 | A kind of preparation method of low cost high stability sulfur-resistant transformation catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Effects of Doping Rare Earth Elements (Y, La, and Ce) on Catalytic Performances of CoMo/MgAlM for Water Gas Shift Reaction;Jinxing Mi et al.;《Ind. Eng. Chem. Res.》;20171228;第57卷;第833-844页 * |
| 炼油废催化剂对劣质污水中有机物吸附性能的研究;张莉等;《工业水处理》;20080531;第28卷(第5期);摘要 * |
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