CN106732792B - A kind of processing coal chemical industry high-salt wastewater catalyst and preparation method thereof - Google Patents
A kind of processing coal chemical industry high-salt wastewater catalyst and preparation method thereof Download PDFInfo
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- CN106732792B CN106732792B CN201611166477.2A CN201611166477A CN106732792B CN 106732792 B CN106732792 B CN 106732792B CN 201611166477 A CN201611166477 A CN 201611166477A CN 106732792 B CN106732792 B CN 106732792B
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a kind of processing coal chemical industry high-salt wastewater catalyst and preparation method thereof.This method comprises the following steps: (1) adhesive being added in alumina powder, obtains catalyst kernel through being granulated；(2) alumina powder, metal salt solution, pore creating material and adhesive are added in the catalyst kernel, through being granulated the shaping of catalyst sphere for obtaining forming wrapping layer outside the catalyst kernel；(3) the shaping of catalyst sphere is dried and is roasted；(4) hydrophobically modified is carried out to the surface of the shaping of catalyst sphere obtained after the roasting, the processing coal chemical industry high-salt wastewater catalyst can be obtained.Catalyst of the present invention is the catalyst using Multimetal oxide as main active component, surface with hydrophobic property, can effectively prevent the Cl in high strong brine‑、SO4 2‑Equal Anion-adsorptions, improve the removal efficiency of catalytic activity and organic matter.
Description
Technical field
The invention belongs to field of catalyst preparation more particularly to a kind of processing coal chemical industry high-salt wastewater catalyst and
Preparation method.
Background technique
Modern Coal-based Chemical refers mainly to coal gas, coal oil, coal-to-olefin, coal-ethylene glycol etc., and Modern Coal-based Chemical is to realize
The important channel that Coal Clean efficiently utilizes is the important directions that country encourages.But since Coal Chemical Engineering Project is mainly distributed on west
Northern ecologically fragile areas, water resources shortage, and without receiving sewage body, therefore waste water requires " nearly zero " discharge.The processing of high-salt wastewater
Disposition is waste water " one of the key restriction factors of nearly zero " discharge.Coal chemical industry high-salt wastewater mostlys come from film concentration or heat is dense
The strong brine that compression process generates, total dissolved solid (TDS) difference is larger, and generally 1%~8%, some is even as high as
20% or more, COD (COD) is 100~2000mg/L, and predominantly hardly degraded organic substance.High COD may cause film
Pollution, evaporation and crystal process organic pollution limit waste water and are further concentrated or resource utilization.For such waste water
Processing, since salinity is to the inhibiting effect of microorganism, biochemical method is generally hard to work.Active carbon adsorption is to organic matter removal
Significant effect, but activated carbon adsorption capacity is limited, and difficulty is regenerated after adsorption saturation, causes operating cost higher.Multiphase ozone is urged
Change oxidizing process by the hydroxyl radical free radical of generation strong oxidizing property, oxygen is carried out to organic pollutant difficult to degrade, high stability in water
Change degradation, does not generate secondary pollution, become one of the key technology of organic pollutant removal in high-salt wastewater.
Correlative study shows the surface soda acid position of metal oxide and surface hydroxyl groups are considered as the work that ozone decomposes
Property site.In high strong brine, due to Cl-、SO4 2-、CO3 2-、PO4 3-The absorption of equal anion, occupies active site, so that smelly
The decline of VPO catalysts activity.Existing ozone catalyst is ineffective for organic matter removal in coal chemical industry high-salt wastewater.
Summary of the invention
The object of the present invention is to provide a kind of processing coal chemical industry high-salt wastewater catalyst and preparation method thereof, this method is logical
The metal active constituent for changing catalyst is crossed, regulates and controls Surface acid-base properties, and obtain using the methods of surfactant-modified
Hydrophobic surface will weaken Cl-、SO4 2-Equal Anion-adsorptions effect, so that ozone catalyst is shown in high-salt wastewater
High COD removal efficiency.
A kind of preparation method handling coal chemical industry high-salt wastewater catalyst provided by the invention, includes the following steps:
(1) adhesive is added in alumina powder, obtains catalyst kernel through being granulated；
(2) alumina powder, metal salt solution, pore creating material and adhesive are added in the catalyst kernel, through being granulated
Obtain the shaping of catalyst sphere that wrapping layer is formed outside the catalyst kernel；
(3) the shaping of catalyst sphere is dried and is roasted；
(4) hydrophobically modified is carried out to the surface of the shaping of catalyst sphere obtained after the roasting, the place can be obtained
Manage coal chemical industry high-salt wastewater catalyst.
Above-mentioned preparation method, in step (1), the mass ratio of the aluminium oxide and described adhesive can be (20~100):
1, concretely 20:1.Described adhesive can be at least one of water, silica solution and Aluminum sol.
The diameter of the catalyst kernel can be 2~4mm, concretely 2~3mm, 3~4mm, 2mm, 3mm or 4mm.
Above-mentioned preparation method, in step (2), the catalyst kernel, the alumina powder, the pore creating material and institute
The weight ratio for stating adhesive is (50%~70%): (20%~30%): (5%~10%): (1%~5%), concretely
(60%~70%): (20%~30%): 5%:5%, 60%:30%:5%:5% or 70%:20%:5%:5%.It is described to make
Hole agent can be at least one of polyethylene glycol, polyvinyl alcohol, urea and carbon black.Described adhesive can be water, silica solution and aluminium
At least one of colloidal sol.
Above-mentioned preparation method, in step (2), the mass volume ratio of the catalyst kernel and the metal salt solution can
For 1g:(0.1~1) mL, concretely 1g:(0.5~1) mL, 1g:0.5mL or 1g:1mL.
The metal salt solution contains manganese salt and following at least one metal salt: cerium salt, magnesium salts and pink salt can specifically contain
There are manganese salt and following any metal salt: cerium salt, magnesium salts and pink salt.The manganese salt and following at least one metal salt: cerium
The molar ratio of salt, magnesium salts and pink salt can be (1~10): 1, concretely (4~10): 1, (5~10): 1, (4~5): 1,4:1,
5:1 or 10:1.The molar concentration of manganese salt can be 0.1~2.0mol/L in the metal salt solution, concretely 1.0mol/L.Institute
Stating metal salt is the metal salt for being dissolvable in water water, including but not limited to nitrate, sulfate, acetate or chlorate.
Above-mentioned preparation method, in step (2), the diameter of the shaping of catalyst sphere can be 4~8mm, concretely 4
~6mm, 6~8mm, 4mm, 6mm or 8mm.
Above-mentioned preparation method, in step (3), the temperature of the drying can be 80~150 DEG C (such as 100 DEG C), the time 4
~12 hours (such as 12 hours)；The temperature of the roasting is 500~900 DEG C (such as 600 DEG C), and the time is that (such as 4 was small in 2~8 hours
When).
Above-mentioned preparation method, in step (4), surface modifier that the hydrophobically modified uses can for surfactant and
At least one of silane coupling agent.The surfactant concretely lauryl sodium sulfate, stearic acid or perfluoro caprylic acid；
The silane coupling agent concretely 3- methacryloxypropyl trimethoxy silane.The method of the hydrophobically modified is this
Conventional method well known to the technical staff of field, the organic solution of surface modifier and/or water-soluble as described in being impregnated in catalyst
In liquid, the hydrophobically modified of catalyst can be realized after drying.The catalyst is in the organic solution and/or aqueous solution
Mass concentration can be 3%~5%, concretely 3% or 5%.
Invention further provides a kind of catalysis of processing coal chemical industry high-salt wastewater that above-mentioned preparation method is prepared
Agent.The hardly degraded organic substance that the catalyst can be used in catalytic ozonation removal coal chemical industry high-salt wastewater, removal efficiency are high.
The invention has the following beneficial effects:
(1) the salt tolerant ozone catalytic oxidation catalyst prepared in the present invention is with Multimetal oxide for main active group
Divide, catalyst of the surface with hydrophobic property, can effectively prevent the Cl in high strong brine-、SO4 2-Equal Anion-adsorptions, raising are urged
Change the removal efficiency of activity and organic matter.
(2) present invention is rolled together with alumina powder powder stock by the way that the metal salt with ozone catalytic activity is dissolved in water
Dynamic to be granulated, is dry, roasting, in high-temperature sintering process, the metal oxide that metal salt decomposes has micron or nanometer ruler
It is very little, it is uniformly distributed in alumina support, adhesive strength is high, and catalytic activity and stability are strong, large-scale industry easy to accomplish
Metaplasia produces.
Catalyst of the invention is mainly used in catalytic ozonation removal coal chemical industry high-salt wastewater (TDS is 1%~8%)
Persistent organic pollutants.
Specific embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Embodiment 1, preparation processing coal chemical industry high-salt wastewater catalyst
Processing coal chemical industry high-salt wastewater catalyst is prepared in accordance with the following steps:
(1) amorphous aluminium powder is selected, the Aluminum sol adhesive of the 5% of the quality of alumina powder is added, through making
Grain obtains the catalyst kernel that diameter is 2mm；
(2) manganese nitrate and cerous nitrate, 4:1 is made into aqueous solution in molar ratio, and wherein manganese nitrate molar concentration is 1.0mol/
L；Metal salt solution (mass volume ratio of catalyst kernel and metal salt solution is 1g:1mL) and alumina powder, poly- second two
Pure and mild Aluminum sol adhesive mixing, is added in pelletizer, (catalyst kernel, alumina powder is granulated together with catalyst kernel
The mass ratio at end, pore creating material and adhesive is 60%:30%:5%:5%, obtains forming wrapping layer outside catalyst kernel
Diameter is the shaping of catalyst sphere of 4mm；
(3) by shaping of catalyst sphere in 100 DEG C of dry 12h, 600 DEG C of roasting 4h；
(4) it is carried out using surface of the Surfactant SDS to the shaping of catalyst sphere being fired hydrophobic
It is modified to obtain processing coal chemical industry high-salt wastewater catalyst.The step of hydrophobically modified, is as follows: lauryl sodium sulfate is dissolved in nothing
Water-ethanol (concentration 5%) will be cleaned up with ethyl alcohol after catalyst dipping 1h, be put into 105 DEG C of oven dryings.
The catalytic performance test of catalyst manufactured in the present embodiment is accomplished by the following way:
Certain coal oil enterprise reverse osmosis concentrated water, TDS 18800mg/L, COD 300mg/ are handled using catalytic ozonation
L, ozone dosage 200mg/L, reaction time 60min are added without ozone catalyst, and COD is reduced to 250mg/ by 300mg/L
L；The salt tolerant ozone catalyst prepared using embodiment 1, COD are reduced to 150mg/L by 300mg/L, and COD removal rate reaches
50%, COD removal rate improve 33.3%.
Embodiment 2, preparation processing coal chemical industry high-salt wastewater catalyst
Processing coal chemical industry high-salt wastewater catalyst is prepared in accordance with the following steps:
(1) amorphous aluminium powder is selected, the Aluminum sol adhesive of the 5% of the quality of alumina powder is added, through making
Grain obtains the catalyst kernel that diameter is 3mm；
(2) manganese sulfate and magnesium sulfate, 10:1 is made into aqueous solution in molar ratio, and wherein manganese sulfate molar concentration is 1.0mol/
L, metal salt solution (mass volume ratio of catalyst kernel and metal salt solution is 1g:1mL) and alumina powder, poly- second two
Pure and mild Aluminum sol adhesive mixing, is added in pelletizer, (catalyst kernel, alumina powder is granulated together with catalyst kernel
The mass ratio at end, pore creating material and adhesive is 70%:20%:5%:5%, obtains forming wrapping layer outside catalyst kernel
Diameter is the shaping of catalyst sphere of 6mm；
(3) by shaping of catalyst sphere in 100 DEG C of dry 12h, 600 DEG C of roasting 4h；
(4) using silane coupling agent 3- methacryloxypropyl trimethoxy silane to the shaping of catalyst being fired
The surface of sphere carries out hydrophobically modified, obtains processing coal chemical industry high-salt wastewater catalyst.The step of hydrophobically modified, is as follows: by silicon
3:4:93 is hydrolyzed for 24 hours after mixing by volume for alkane coupling agent and dehydrated alcohol, water, will be clear with ethyl alcohol after catalyst dipping 1h
Wash clean is put into 105 DEG C of oven dryings.
The catalytic performance test of catalyst manufactured in the present embodiment is accomplished by the following way:
Certain high strong brine of coal gas enterprise, TDS 80000mg/L, COD 1500mg/ are handled using catalytic ozonation
L, ozone dosage 500mg/L, reaction time 60min are added without ozone catalyst, and COD is reduced to by 1500mg/L
1300mg/L；The salt tolerant ozone catalyst prepared using embodiment 2, COD are reduced to 1100mg/L, COD removal by 1500mg/L
Efficiency improves 13.3%.
Embodiment 3, preparation processing coal chemical industry high-salt wastewater catalyst
Processing coal chemical industry high-salt wastewater catalyst is prepared in accordance with the following steps:
(1) amorphous aluminium powder is selected, the Aluminum sol adhesive of the 5% of the quality of alumina powder is added, through making
Grain obtains the catalyst kernel that diameter is 3mm；
(2) manganese acetate and tin tetrachloride, 5:1 is made into aqueous solution in molar ratio, and wherein manganese acetate molar concentration is
1.0mol/L, metal salt solution (mass volume ratio of catalyst kernel and metal salt solution is 1g:0.5mL) and alumina powder
End, polyethylene glycol and the mixing of Aluminum sol adhesive, are added in pelletizer, be granulated together with catalyst kernel (catalyst kernel,
The mass ratio of alumina powder, pore creating material and adhesive is 70%:20%:5%:5%, obtains being formed outside catalyst kernel
The diameter of wrapping layer is the shaping of catalyst sphere of 6mm；
(3) by shaping of catalyst sphere in 100 DEG C of dry 12h, 600 DEG C of roasting 4h；
(4) hydrophobically modified is carried out using surface of the surfactant stearic acid to the shaping of catalyst sphere after being fired,
Obtain processing coal chemical industry high-salt wastewater catalyst.The step of hydrophobically modified is as follows: stearic acid is dissolved in acetone, and (concentration is
5%) it, will be cleaned up after catalyst dipping 1h with acetone, be put into 105 DEG C of oven dryings.
The catalytic performance test of salt tolerant ozone catalyst manufactured in the present embodiment is accomplished by the following way:
Certain high strong brine of coal-to-olefin enterprise, TDS 42800mg/L, COD 500mg/ are handled using catalytic ozonation
L, ozone dosage 500mg/L, reaction time 60min are added without ozone catalyst, and COD is reduced to 350mg/ by 500mg/L
L；Benefit catalyst prepared with embodiment 3, COD are reduced to 200mg/L by 500mg/L, and COD removal efficiency improves 30.0%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes made without departing from the spirit and principles of the present invention, should be equivalent substitute mode,
It is included in the present invention.
Claims (7)
1. a kind of preparation method for handling coal chemical industry high-salt wastewater catalyst, includes the following steps:
(1) adhesive is added in alumina powder, obtains catalyst kernel through being granulated；
(2) alumina powder, metal salt solution, pore creating material and adhesive are added in the catalyst kernel, is obtained through being granulated
The shaping of catalyst sphere of wrapping layer is formed outside the catalyst kernel；
In step (2), the mass volume ratio of the catalyst kernel and the metal salt solution is 1g:(0.1 ~ 1) mL；The gold
Belong to salting liquid and contains manganese salt and following at least one metal salt: cerium salt, magnesium salts and pink salt；The manganese salt and following at least one
Metal salt: the molar ratio of cerium salt, magnesium salts and pink salt be (1 ~ 10): 1；The molar concentration of manganese salt is in the metal salt solution
0.1~2.0mol/L；
(3) the shaping of catalyst sphere is dried and is roasted；
(4) hydrophobically modified is carried out to the surface of the shaping of catalyst sphere obtained after the roasting, the processing coal can be obtained
Chemical industry high-salt wastewater catalyst；
In step (4), the hydrophobically modified uses lauryl sodium sulfate, stearic acid, perfluoro caprylic acid and 3- methacryloxypropyl
At least one of base propyl trimethoxy silicane.
2. preparation method according to claim 1, it is characterised in that: in step (1), the matter of the aluminium oxide and adhesive
Amount is than being (20 ~ 100): 1；Described adhesive is at least one of water, silica solution and Aluminum sol.
3. preparation method according to claim 1 or 2, it is characterised in that: in step (1), the catalyst kernel it is straight
Diameter is 2 ~ 4mm.
4. preparation method according to claim 1 or 2, it is characterised in that: the catalyst kernel, described in step (2)
The weight ratio of alumina powder, the pore creating material and described adhesive is (60% ~ 70%): (20% ~ 30%): (5% ~ 10%): (1%
~ 5%)；The pore creating material is at least one of polyethylene glycol, polyvinyl alcohol, urea and carbon black；Described adhesive is water, silicon is molten
At least one of glue and Aluminum sol.
5. preparation method according to claim 1 or 2, it is characterised in that: in step (2), the shaping of catalyst sphere
Diameter be 4 ~ 8mm.
6. preparation method according to claim 1 or 2, it is characterised in that: in step (3), the temperature of the drying is 80 ~
150 DEG C, the time is 4 ~ 12 hours；The temperature of the roasting is 500 ~ 900 DEG C, and the time is 2 ~ 8 hours.
7. the processing coal chemical industry high-salt wastewater catalyst that preparation method of any of claims 1-6 is prepared.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108178283A (en) * | 2017-12-27 | 2018-06-19 | 苏州大学 | The method for removing organic matter in high-chloride wastewater |
| CN109772358A (en) * | 2018-06-29 | 2019-05-21 | 光大水务（深圳）有限公司 | A kind of preparation method of catalyst pore creating material and the high porosity catalyst based on pore creating material |
| CN108745419B (en) * | 2018-07-24 | 2020-12-18 | 萍乡煤科环保科技有限公司 | Catalyst for catalyzing ozone to oxidize wastewater and preparation method thereof |
| CN109939695B (en) * | 2019-04-03 | 2022-03-22 | 宁夏大学 | Load type O3Preparation of catalyst and application of catalyst in removal of COD (chemical oxygen demand) of high-salinity wastewater in coal chemical industry |
| CN111013571A (en) * | 2019-11-27 | 2020-04-17 | 萍乡煤科环保科技有限公司 | Preparation method of modified ozone catalyst suitable for high-salinity wastewater in coal chemical industry |
| CN110961118B (en) * | 2019-12-18 | 2023-02-24 | 煤炭科学技术研究院有限公司 | Coal gangue-based ozone oxidation catalyst and preparation method and application thereof |
| CN111468105B (en) * | 2020-04-23 | 2023-06-16 | 光大水务科技发展（南京）有限公司 | Multi-layer structure catalyst for catalytic oxidation of nbsCOD by ozone and preparation method and application thereof |
| CN113976118A (en) * | 2021-11-30 | 2022-01-28 | 昂星新型碳材料常州有限公司 | Ozone catalyst, preparation method and application thereof |
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