CN108159871A - A kind of preparation method of composite desulfurizing agent - Google Patents
A kind of preparation method of composite desulfurizing agent Download PDFInfo
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- CN108159871A CN108159871A CN201711492009.9A CN201711492009A CN108159871A CN 108159871 A CN108159871 A CN 108159871A CN 201711492009 A CN201711492009 A CN 201711492009A CN 108159871 A CN108159871 A CN 108159871A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
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Abstract
The present invention relates to desulfurizing agent technical fields, and in particular to a kind of preparation method of composite desulfurizing agent.The present invention carries out acidleach by hydrochloric acid to hornet's nest first,By being carbonized in advance, the thermal decomposition preliminary to the substance progress in hornet's nest is also increased by predecomposition to adsorption capacity simultaneously,Surface-active is then carried out by surfactant,And it is impregnated using phosphoric acid,Increase micro P elements,Have additional nutrients substance,The adsorption capacity to sulphur is also further improved simultaneously,The substances such as surface of oil storage tank iron rust are reused as bacterium source,Screening enrichment culture is carried out to bacterium source,Acquisition can be with desulfurization and the strain corroded to iron,By being loaded to strain,Strain is made to be deposited on carrier,And spray into iron powder,Iron powder is converted by the activity of microorganism when reusing,Increase desulfuration efficiency,Sodium alginate soln is with polyallylamine under the action of calcium ion,Carrier is wrapped up,Absorption and the retention effect to sulphur are improved simultaneously,And improve Sulfur capacity.
Description
Technical field
The present invention relates to desulfurizing agent technical fields, and in particular to a kind of preparation method of composite desulfurizing agent.
Background technology
Many occasions in industrial production can all generate sulfide.Such as, industrial chemicals is being produced with coal or oil
In production process and in the waste water or exhaust gas of general industry production discharge.Wherein, chemical industry original is being produced with coal or oil
In the production process of material, the hydrogen sulfide generated is mainly due to containing more sulphur-containing substance in raw material so that the sulfur-bearing object
Matter reacts and releases hydrogen sulfide in process of production, so as to directly result in catalyst activity substance in subsequent production workshop section
Poisoning and deactivation.In addition, hydrogen sulfide sulfides contained in the waste water or exhaust gas that are discharged in industrial production, if directly arranged
Environment will be seriously affected, even causes person poultry poisoning.
At present, researcher is in order to efficiently reduce destruction of the above-mentioned sulfide to industrial production and environment, for de-
The research and development of sulphur agent give enough attention.Desulfurizing agent various types of the prior art, it is most to be aoxidized with Fe-series desulfurizing agent, manganese
Based on object desulfurizing agent, solid base or liquid base desulfurizing agent, activated carbon desulphurization agent or molecular sieve active metal desulfurizing agent.Wherein,
Fe-series desulfurizing agent is one of more traditional desulfurizing agent, and the type desulfurizing agent is mainly the activity using ferriferous oxide as desulfurizing agent
Component.
Ferric oxide desulfurizer is strip porous structure solid, is divided into two kinds of non-mixed oxide and mixed oxide.The former
Mainly by aqueous Fe2O3Composition, the latter mainly by manually croci be loaded in that specific surface is big and the material of short texture such as
The compounding substances formed on rice husk, sawdust etc..Ferric oxide desulfurizer carries out quick irreversible chemical absorption to vulcanization Hydrogen Energy,
Iron oxide is converted into iron sulfide.When being contacted with oxygen, iron sulfide is oxidized to free sulfur and iron oxide, this for desulfurizing agent again
Raw, desulfurization regeneration is recycled repeatedly, until pore is inactivated by sulphur blocking in desulfurizing agent.Due in actual production, with a large amount of
FeS generation, prevent desulfurizing agent to a certain extent from regenerating.In addition, there are the SO of part in industrial gasses2Gas, with
Fe2O3Unrenewable FeSO is generated under certain condition4And Fe2(SO4)3.In summary factor is included in final waste desulfurizing agent
Elemental sulfur, FeS, Fe2S3、FeSO4And Fe2(SO4)3Wait mixtures.With the increase of ferric oxide desulfurizer dosage, one containing big
The new pollution sources of amount noxious material are also increasingly formed.
In conclusion used ferric oxide desulfurizer is primarily present the defects of following currently on the market：Preparation process answers
It is miscellaneous, the production cycle is long, and the Sulfur capacity for the ferric oxide desulfurizer prepared is generally all relatively low, mechanical strength is also poor, and contains one
Quantitative harmful substance easily causes harm to environment and human body.
Therefore, we it is necessary to again prepare a kind of novel desulfurizing agent, solved nowadays in the market with this
The problems of desulfurizing agent is preferably adapted to the demand of social fish relevant department, this hair that will push China's industry significantly
Exhibition, is a very significant thing.
Invention content
The technical problems to be solved by the invention：It is low for current used ferric oxide desulfurizer Sulfur capacity, and contain one
Quantitative harmful substance easily causes the problem of endangering to environment and human body, and the present invention provides a kind of preparations of composite desulfurizing agent
Method.
In order to solve the above technical problems, the present invention is using technical solution as described below：
A kind of preparation method of composite desulfurizing agent, the preparation method include the following steps：
（1）In mass ratio 1:4, hornet's nest with hydrochloric acid solution is uniformly mixed, and carry out ultrasonic vibration, takes out the hornet after concussion
Nest is placed in drying in baking oven, places into carbide furnace and is carbonized in advance, take pre- carbide, by pre- carbide, phosphoric acid solution and table
Face activating agent mixing, stands, filtering, collects filtrate, dry, collects dried object；
（2）Dried object is immersed in glucose solution, takes out the dried object after impregnating, air-dries, obtains carrier, it is spare, by quality
Than 4~6:9:1~3, surface of oil storage tank iron rust, oil drilling waste liquid and pool carp louse is taken to be put into grinding mill and mill, collects and grinds
Grind object；
（3）To mill object and nutrient solution in mass ratio 1:3 are uniformly mixed, and are put into container, and temperature is 30~33 in holding container
DEG C, 1~3 day is stood, is stirred, filtered fluid is collected in filtering；
（4）By step（2）Spare carrier in mass ratio 1:4~6 are uniformly mixed with filtered fluid, stand, and take out the load after standing
Body air-dries, obtains composite desulfurizing agent matrix, iron powder is sprayed into compound desulfurization matrix using high-pressure spray gun, straying quatity is multiple for every gram
Close the iron powder that desulfurization matrix sprays into 20~30mg；
（5）After iron powder penetrating, the composite desulfurizing agent matrix of iron powder and mixed liquor in mass ratio 1 will be sprayed into:2~4, mixing is equal
It is even, 10~15h is stood at 20~26 DEG C, then the composite desulfurizing agent matrix for spraying into iron powder is taken out, be placed in cold at -10~-7 DEG C
Freeze 3~5h, collect frozen material, crush, sieving particle is collected in sieving；
（6）It will sieving particle and calcium chloride solution in mass ratio 1:3 are stirred in blender, collect stirring mixture, cold
Be lyophilized it is dry, collect freeze-drying object to get composite desulfurizing agent.
The step（1）In the process that is carbonized in advance be to be warming up to 90~95 DEG C with 5 DEG C/min, keep the temperature 40~50min, then with
8 DEG C/min is warming up to 110~130 DEG C, and be carbonized 1~3h in advance.
The step（1）Described in surfactant for hexadecyldimethyl benzyl ammonium ammonia bromide, fatty acid methyl ester ethoxylation
Any one in object sulfonate, the mass ratio of pre- carbide, phosphoric acid solution and surfactant is 3~5:8:0.4.
The step（3）Middle nutrient solution to count in parts by weight, take 60~70 parts of water, 30~33 parts of yeast extracts, 24~
27 parts of peptones, 12~14 parts of ammonium sulfate, 6~13 parts of sodium chloride, 4~7 parts of magnesium nitrates and 1~3 part of ferric citrate stirring are equal
Even, sterilizing is to get nutrient solution.
The step（5）Middle mixed liquor in mass ratio 3~5:1, sodium alginate soln is uniformly mixed with polyallylamine,
Up to mixed liquor.
Compared with other methods, advantageous effects are the present invention：
The present invention carries out hornet's nest acidleach by hydrochloric acid first, on the one hand removes the impurity in hornet's nest, on the other hand increases
Voidage in hornet's nest then carries out the substance in hornet's nest preliminary thermal decomposition by being carbonized in advance, makes the objects such as macromolecule
Matter carries out preliminary exposition, and the substance being decomposed to form is allow to increase the offer to nutrition, while is also increased pair by predecomposition
Adsorption capacity is then carried out surface-active by surfactant and is impregnated using phosphoric acid, increases micro P elements,
Have additional nutrients substance, while also further improves the adsorption capacity to sulphur, reuses the substances such as surface of oil storage tank iron rust as bacterium
Source, carries out bacterium source screening enrichment culture, and acquisition, by being loaded to strain, can be made with desulfurization and the strain corroded to iron
Strain is deposited on carrier, and sprays into iron powder, and iron powder is converted by the activity of microorganism when reusing, increases desulfurization
Efficiency, sodium alginate soln under the action of calcium ion, wrap up carrier with polyallylamine, while improve the suction to sulphur
Attached and retention effect, and improve Sulfur capacity.
Figure of description
Fig. 1 is the desulfurization extracting rate weightening value line chart of the composite desulfurizing agent of the present invention.
Specific embodiment
The selection of surfactant：Hexadecyldimethyl benzyl ammonium ammonia bromide, fatty acid methyl ester ethoxylate sulfonate（It chooses
It is praised and new material Science and Technology Ltd. in Ningbo）In any one.
The preparation of nutrient solution：It counts in parts by weight, takes 60~70 parts of water, 30~33 parts of yeast extracts, 24~27 parts of albumen
Peptone, 12~14 parts of ammonium sulfate, 6~13 parts of sodium chloride, 4~7 parts of magnesium nitrates and 1~3 part of ferric citrate stir evenly, and sterilization disappears
Poison is to get nutrient solution.
The preparation of mixed liquor：In mass ratio 3~5:1, mass fraction is mixed for 3% sodium alginate soln with polyallylamine
It closes uniformly to get mixed liquor.
Oil drilling waste liquid：It is taken from Daqing oil field.
A kind of preparation method of composite desulfurizing agent, the preparation method include the following steps：
（1）In mass ratio 1:4, hornet's nest with 1.3mol/L hydrochloric acid solutions is uniformly mixed, and carry out ultrasonic vibration 15min, is taken
The hornet's nest gone out after concussion is placed in 60 DEG C of baking ovens dry 5h, places into carbide furnace and is carbonized in advance, the process being carbonized in advance is
90~95 DEG C are warming up to 5 DEG C/min, keep the temperature 40~50min, then be warming up to 110~130 DEG C with 8 DEG C/min, it is carbonized 1 in advance~
3h takes pre- carbide, is 3~5 by pre- carbide, 1.1mol/L phosphoric acid solutions and surfactant mass ratio in mass ratio:8:
0.4 mixing stands 3~5h at room temperature, and filtrate is collected in filtering, dry, collects dried object；
（2）Dried object is immersed in 4h in 1.3mol/L glucose solutions, takes out the dried object after impregnating, air-dries, obtains carrier, it is standby
With in mass ratio 4~6:9:1~3, surface of oil storage tank iron rust, oil drilling waste liquid and pool carp louse is taken to be put into grinding mill with 800r/
Min carries out the 30min that mills, and collects object of milling；
（3）To mill object and nutrient solution in mass ratio 1:3 are uniformly mixed, and are put into container, and temperature is 30~33 in holding container
DEG C, 1~3 day is stood, is stirred, filtered fluid is collected in filtering；
（4）By step（2）Spare carrier in mass ratio 1:4~6 are uniformly mixed with filtered fluid, stand 6h, take out after standing
Carrier air-dries, obtains composite desulfurizing agent matrix, 500 mesh iron powders are sprayed into compound desulfurization matrix using high-pressure spray gun, straying quatity is
Every gram of compound desulfurization matrix sprays into the 500 mesh iron powders of 20~30mg；
（5）After iron powder penetrating, the composite desulfurizing agent matrix of iron powder and mixed liquor in mass ratio 1 will be sprayed into:2~4, mixing is equal
It is even, 10~15h is stood at 20~26 DEG C, then the composite desulfurizing agent matrix for spraying into iron powder is taken out, be placed in cold at -10~-7 DEG C
Freeze 3~5h, collect frozen material, crush, sieving particle is collected in sieving；
（6）It will sieving particle and 0.7mol/L calcium chloride solutions in mass ratio 1:3 are stirred in blender, and it is mixed to collect stirring
Object is closed, freeze-drying collects freeze-drying object to get composite desulfurizing agent.
Embodiment 1
The selection of surfactant：Hexadecyldimethyl benzyl ammonium ammonia bromide.
The preparation of nutrient solution：It counts in parts by weight, takes 60 parts of water, 30 parts of yeast extracts, 24 parts of peptones, 12 parts of sulfuric acid
Ammonium, 6 parts of sodium chloride, 4 parts of magnesium nitrates and 1 part of ferric citrate stir evenly, and sterilizing is to get nutrient solution.
The preparation of mixed liquor：In mass ratio 3:1, mass fraction is mixed for 3% sodium alginate soln with polyallylamine
Uniformly to get mixed liquor.
Oil drilling waste liquid：It is taken from Daqing oil field.
A kind of preparation method of composite desulfurizing agent, the preparation method include the following steps：
（1）In mass ratio 1:4, hornet's nest with 1.3mol/L hydrochloric acid solutions is uniformly mixed, and carry out ultrasonic vibration 15min, is taken
The hornet's nest gone out after concussion is placed in 60 DEG C of baking ovens dry 5h, places into carbide furnace and is carbonized in advance, the process being carbonized in advance is
90 DEG C are warming up to 5 DEG C/min, keeps the temperature 40min, then 110 DEG C are warming up to 8 DEG C/min, be carbonized 1h in advance, takes pre- carbide, will be pre-
Carbide, 1.1mol/L phosphoric acid solutions and surfactant mass ratio in mass ratio are 3:8:0.4 mixing, stands at room temperature
Filtrate is collected in 3h, filtering, dry, collects dried object；
（2）Dried object is immersed in 4h in 1.3mol/L glucose solutions, takes out the dried object after impregnating, air-dries, obtains carrier, it is standby
With in mass ratio 4:9:1, surface of oil storage tank iron rust, oil drilling waste liquid and pool carp louse is taken to be put into grinding mill with 800r/min into
The capable 30min that mills, collects object of milling；
（3）To mill object and nutrient solution in mass ratio 1:3 are uniformly mixed, and are put into container, and temperature is 30 DEG C in holding container, quiet
It puts 1 day, stirs, filtered fluid is collected in filtering；
（4）By step（2）Spare carrier in mass ratio 1:4 are uniformly mixed with filtered fluid, stand 6h, take out the load after standing
Body air-dries, obtains composite desulfurizing agent matrix, 500 mesh iron powders are sprayed into compound desulfurization matrix using high-pressure spray gun, straying quatity is every
Gram compound desulfurization matrix sprays into the 500 mesh iron powders of 20mg；
（5）After iron powder penetrating, the composite desulfurizing agent matrix of iron powder and mixed liquor in mass ratio 1 will be sprayed into:2, it is uniformly mixed,
10h is stood at 20 DEG C, then the composite desulfurizing agent matrix for spraying into iron powder is taken out, is placed at -10 DEG C and freezes 3h, collect frozen material,
It crushes, sieving, collects sieving particle；
（6）It will sieving particle and 0.7mol/L calcium chloride solutions in mass ratio 1:3 are stirred in blender, and it is mixed to collect stirring
Object is closed, freeze-drying collects freeze-drying object to get composite desulfurizing agent.
Embodiment 2
The selection of surfactant：Hexadecyldimethyl benzyl ammonium ammonia bromide.
The preparation of nutrient solution：It counts in parts by weight, takes 65 parts of water, 32 parts of yeast extracts, 25 parts of peptones, 13 parts of sulfuric acid
Ammonium, 10 parts of sodium chloride, 5 parts of magnesium nitrates and 2 parts of ferric citrates stir evenly, and sterilizing is to get nutrient solution.
The preparation of mixed liquor：In mass ratio 4:1, mass fraction is mixed for 3% sodium alginate soln with polyallylamine
Uniformly to get mixed liquor.
Oil drilling waste liquid：It is taken from Daqing oil field.
A kind of preparation method of composite desulfurizing agent, the preparation method include the following steps：
（1）In mass ratio 1:4, hornet's nest with 1.3mol/L hydrochloric acid solutions is uniformly mixed, and carry out ultrasonic vibration 15min, is taken
The hornet's nest gone out after concussion is placed in 60 DEG C of baking ovens dry 5h, places into carbide furnace and is carbonized in advance, the process being carbonized in advance is
92 DEG C are warming up to 5 DEG C/min, keeps the temperature 42min, then 125 DEG C are warming up to 8 DEG C/min, be carbonized 2h in advance, takes pre- carbide, will be pre-
Carbide, 1.1mol/L phosphoric acid solutions and surfactant mass ratio in mass ratio are 4:8:0.4 mixing, stands at room temperature
Filtrate is collected in 4h, filtering, dry, collects dried object；
（2）Dried object is immersed in 4h in 1.3mol/L glucose solutions, takes out the dried object after impregnating, air-dries, obtains carrier, it is standby
With in mass ratio 6:9:2, surface of oil storage tank iron rust, oil drilling waste liquid and pool carp louse is taken to be put into grinding mill with 800r/min into
The capable 30min that mills, collects object of milling；
（3）To mill object and nutrient solution in mass ratio 1:3 are uniformly mixed, and are put into container, and temperature is 32 DEG C in holding container, quiet
It puts 2 days, stirs, filtered fluid is collected in filtering；
（4）By step（2）Spare carrier in mass ratio 1:5 are uniformly mixed with filtered fluid, stand 6h, take out the load after standing
Body air-dries, obtains composite desulfurizing agent matrix, 500 mesh iron powders are sprayed into compound desulfurization matrix using high-pressure spray gun, straying quatity is every
Gram compound desulfurization matrix sprays into the 500 mesh iron powders of 25mg；
（5）After iron powder penetrating, the composite desulfurizing agent matrix of iron powder and mixed liquor in mass ratio 1 will be sprayed into:3, it is uniformly mixed,
12h is stood at 23 DEG C, then the composite desulfurizing agent matrix for spraying into iron powder is taken out, is placed at -8 DEG C and freezes 5h, collect frozen material, powder
Broken, sieving particle is collected in sieving；
（6）It will sieving particle and 0.7mol/L calcium chloride solutions in mass ratio 1:3 are stirred in blender, and it is mixed to collect stirring
Object is closed, freeze-drying collects freeze-drying object to get composite desulfurizing agent.
Embodiment 3
The selection of surfactant：Fatty acid methyl ester ethoxylate sulfonate（Choose praised in Ningbo it is limited with new material science and technology
Company）.
The preparation of nutrient solution：It counts in parts by weight, takes 70 parts of water, 33 parts of yeast extracts, 27 parts of peptones, 14 parts of sulfuric acid
Ammonium, 13 parts of sodium chloride, 7 parts of magnesium nitrates and 3 parts of ferric citrates stir evenly, and sterilizing is to get nutrient solution.
The preparation of mixed liquor：In mass ratio 5:1, mass fraction is mixed for 3% sodium alginate soln with polyallylamine
Uniformly to get mixed liquor.
Oil drilling waste liquid：It is taken from Daqing oil field.
A kind of preparation method of composite desulfurizing agent, the preparation method include the following steps：
（1）In mass ratio 1:4, hornet's nest with 1.3mol/L hydrochloric acid solutions is uniformly mixed, and carry out ultrasonic vibration 15min, is taken
The hornet's nest gone out after concussion is placed in 60 DEG C of baking ovens dry 5h, places into carbide furnace and is carbonized in advance, the process being carbonized in advance is
95 DEG C are warming up to 5 DEG C/min, keeps the temperature 50min, then 130 DEG C are warming up to 8 DEG C/min, be carbonized 3h in advance, takes pre- carbide, will be pre-
Carbide, 1.1mol/L phosphoric acid solutions and surfactant mass ratio in mass ratio are 5:8:0.4 mixing, stands at room temperature
Filtrate is collected in 5h, filtering, dry, collects dried object；
（2）Dried object is immersed in 4h in 1.3mol/L glucose solutions, takes out the dried object after impregnating, air-dries, obtains carrier, it is standby
With in mass ratio 6:9:3, surface of oil storage tank iron rust, oil drilling waste liquid and pool carp louse is taken to be put into grinding mill with 800r/min into
The capable 30min that mills, collects object of milling；
（3）To mill object and nutrient solution in mass ratio 1:3 are uniformly mixed, and are put into container, and temperature is 33 DEG C in holding container, quiet
It puts 3 days, stirs, filtered fluid is collected in filtering；
（4）By step（2）Spare carrier in mass ratio 1:6 are uniformly mixed with filtered fluid, stand 6h, take out the load after standing
Body air-dries, obtains composite desulfurizing agent matrix, 500 mesh iron powders are sprayed into compound desulfurization matrix using high-pressure spray gun, straying quatity is every
Gram compound desulfurization matrix sprays into the 500 mesh iron powders of 30mg；
（5）After iron powder penetrating, the composite desulfurizing agent matrix of iron powder and mixed liquor in mass ratio 1 will be sprayed into:4, it is uniformly mixed,
15h is stood at 26 DEG C, then the composite desulfurizing agent matrix for spraying into iron powder is taken out, is placed at -7 DEG C and freezes 5h, collect frozen material, powder
Broken, sieving particle is collected in sieving；
（6）It will sieving particle and 0.7mol/L calcium chloride solutions in mass ratio 1:3 are stirred in blender, and it is mixed to collect stirring
Object is closed, freeze-drying collects freeze-drying object to get composite desulfurizing agent.
Comparative example 1
The selection of surfactant：Fatty acid methyl ester ethoxylate sulfonate（Choose praised in Ningbo it is limited with new material science and technology
Company）.
The preparation of nutrient solution：It counts in parts by weight, takes 70 parts of water, 33 parts of yeast extracts, 27 parts of peptones, 14 parts of sulfuric acid
Ammonium, 13 parts of sodium chloride, 7 parts of magnesium nitrates and 3 parts of ferric citrates stir evenly, and sterilizing is to get nutrient solution.
The preparation of mixed liquor：In mass ratio 5:1, mass fraction is mixed for 3% sodium alginate soln with polyallylamine
Uniformly to get mixed liquor.
Oil drilling waste liquid：It is taken from Daqing oil field.
A kind of preparation method of composite desulfurizing agent, the preparation method include the following steps：
（1）In mass ratio 1:4, hornet's nest with 1.3mol/L hydrochloric acid solutions is uniformly mixed, and carry out ultrasonic vibration 15min, is taken
The hornet's nest gone out after concussion is placed in 60 DEG C of baking ovens dry 5h, places into carbide furnace and is carbonized in advance, the process being carbonized in advance is
95 DEG C are warming up to 5 DEG C/min, keeps the temperature 50min, then 130 DEG C are warming up to 8 DEG C/min, be carbonized 3h in advance, takes pre- carbide, will be pre-
Carbide, 1.1mol/L phosphoric acid solutions and surfactant mass ratio in mass ratio are 5:8:0.4 mixing, stands at room temperature
Filtrate is collected in 5h, filtering, dry, collects dried object；
（2）Dried object is immersed in 4h in 1.3mol/L glucose solutions, takes out the dried object after impregnating, air-dries, obtains carrier, it is standby
With in mass ratio 6:9:3, surface of oil storage tank iron rust, oil drilling waste liquid and pool carp louse is taken to be put into grinding mill with 800r/min into
The capable 30min that mills, collects object of milling；
（3）To mill object and nutrient solution in mass ratio 1:3 are uniformly mixed, and are put into container, and temperature is 33 DEG C in holding container, quiet
It puts 3 days, stirs, filtered fluid is collected in filtering；
（4）By step（2）Spare carrier in mass ratio 1:6 are uniformly mixed with filtered fluid, stand 6h, take out the load after standing
Body air-dries, obtains composite desulfurizing agent matrix.
Comparative example 2
The selection of surfactant：Fatty acid methyl ester ethoxylate sulfonate（Choose praised in Ningbo it is limited with new material science and technology
Company）.
The preparation of nutrient solution：It counts in parts by weight, takes 70 parts of water, 33 parts of yeast extracts, 27 parts of peptones, 14 parts of sulfuric acid
Ammonium, 13 parts of sodium chloride, 7 parts of magnesium nitrates and 3 parts of ferric citrates stir evenly, and sterilizing is to get nutrient solution.
The preparation of mixed liquor：In mass ratio 5:1, mass fraction is mixed for 3% sodium alginate soln with polyallylamine
Uniformly to get mixed liquor.
Oil drilling waste liquid：It is taken from Daqing oil field.
A kind of preparation method of composite desulfurizing agent, the preparation method include the following steps：
（1）In mass ratio 1:4, hornet's nest with 1.3mol/L hydrochloric acid solutions is uniformly mixed, and carry out ultrasonic vibration 15min, is taken
The hornet's nest gone out after concussion is placed in 60 DEG C of baking ovens dry 5h, places into carbide furnace and is carbonized in advance, the process being carbonized in advance is
95 DEG C are warming up to 5 DEG C/min, keeps the temperature 50min, then 130 DEG C are warming up to 8 DEG C/min, be carbonized 3h in advance, takes pre- carbide, will be pre-
Carbide, 1.1mol/L phosphoric acid solutions and surfactant mass ratio in mass ratio are 5:8:0.4 mixing, stands at room temperature
Filtrate is collected in 5h, filtering, dry, collects dried object；
（2）Dried object is immersed in 4h in 1.3mol/L glucose solutions, takes out the dried object after impregnating, air-dries, obtains carrier, it is standby
With in mass ratio 6:9:3, surface of oil storage tank iron rust, oil drilling waste liquid and pool carp louse is taken to be put into grinding mill with 800r/min into
The capable 30min that mills, collects object of milling；
（3）To mill object and nutrient solution in mass ratio 1:3 are uniformly mixed, and are put into container, and temperature is 33 DEG C in holding container, quiet
It puts 3 days, stirs, filtered fluid is collected in filtering；
（4）By step（2）Spare carrier in mass ratio 1:6 are uniformly mixed with filtered fluid, stand 6h, take out the load after standing
Body air-dries, obtains composite desulfurizing agent matrix, 500 mesh iron powders are sprayed into compound desulfurization matrix using high-pressure spray gun, straying quatity is every
Gram compound desulfurization matrix sprays into the 500 mesh iron powders of 30mg.
Comparative example 3：The desulfurizing agent of Henan alloy Co., Ltd production
Method：The sulfide waste material gone out by plant produced of equal portions is taken to be divided into 4 groups, sample is carried out using U.S.'s Cahn Instruments
Vulcanization experiment, test temperature be 300 DEG C, test period 160min, H2The content of S is 3. 8%, and setting nitrogen is as balance
Gas.
According to the regulation of standard GB/T3795-1996, activity is carried out with the desulfurizing agent prepared by comparative example to embodiment and is commented
Valency detects its Sulfur capacity, mechanical strength and the rate of body weight gain of sulfur material deviate from, and the quality of its performance is characterized with this.
The specific detection case of desulfurizing agent such as table 1 and such as Fig. 1
Table 1
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Sulfur capacity（%） | 42 | 54.2 | 60 | 40 | 37.8 | 32 |
| Mechanical strength（N/cm） | 60 | 65 | 75 | 57 | 42 | 37 |
From the foregoing, it will be observed that the desulfurizing agent Sulfur capacity prepared by the present invention is big, high mechanical strength, and preparation method is simple to operation, is one
The preparation method of kind safety and efficient desulfurizing agent, is worthy to be popularized and uses.
Claims (5)
1. a kind of preparation method of composite desulfurizing agent, which is characterized in that the preparation method includes the following steps：
（1）In mass ratio 1:4, hornet's nest with hydrochloric acid solution is uniformly mixed, and carry out ultrasonic vibration, takes out the hornet after concussion
Nest is placed in drying in baking oven, places into carbide furnace and is carbonized in advance, take pre- carbide, by pre- carbide, phosphoric acid solution and table
Face activating agent mixing, stands, filtering, collects filtrate, dry, collects dried object；
（2）Dried object is immersed in glucose solution, takes out the dried object after impregnating, air-dries, obtains carrier, it is spare, by quality
Than 4~6:9:1~3, surface of oil storage tank iron rust, oil drilling waste liquid and pool carp louse is taken to be put into grinding mill and mill, collects and grinds
Grind object；
（3）To mill object and nutrient solution in mass ratio 1:3 are uniformly mixed, and are put into container, and temperature is 30~33 in holding container
DEG C, 1~3 day is stood, is stirred, filtered fluid is collected in filtering；
（4）By step（2）Spare carrier in mass ratio 1:4~6 are uniformly mixed with filtered fluid, stand, and take out the load after standing
Body air-dries, obtains composite desulfurizing agent matrix, iron powder is sprayed into compound desulfurization matrix using high-pressure spray gun, straying quatity is multiple for every gram
Close the iron powder that desulfurization matrix sprays into 20~30mg；
（5）After iron powder penetrating, the composite desulfurizing agent matrix of iron powder and mixed liquor in mass ratio 1 will be sprayed into:2~4, mixing is equal
It is even, 10~15h is stood at 20~26 DEG C, then the composite desulfurizing agent matrix for spraying into iron powder is taken out, be placed in cold at -10~-7 DEG C
Freeze 3~5h, collect frozen material, crush, sieving particle is collected in sieving；
（6）It will sieving particle and calcium chloride solution in mass ratio 1:3 are stirred in blender, collect stirring mixture, cold
Be lyophilized it is dry, collect freeze-drying object to get composite desulfurizing agent.
2. the preparation method of composite desulfurizing agent according to claim 1, which is characterized in that the step（1）In be in advance carbonized
Process is to be warming up to 90~95 DEG C with 5 DEG C/min, keeps the temperature 40~50min, then be warming up to 110~130 DEG C with 8 DEG C/min, pre- carbon
Change 1~3h.
3. the preparation method of composite desulfurizing agent according to claim 1, which is characterized in that the step（1）Described in surface
Any one of activating agent for hexadecyldimethyl benzyl ammonium ammonia bromide, in fatty acid methyl ester ethoxylate sulfonate, pre- carbide,
The mass ratio of phosphoric acid solution and surfactant is 3~5:8:0.4.
4. the preparation method of composite desulfurizing agent according to claim 1, which is characterized in that the step（3）Middle nutrient solution is
Count in parts by weight, take 60~70 parts of water, 30~33 parts of yeast extracts, 24~27 parts of peptones, 12~14 parts of ammonium sulfate, 6~
13 parts of sodium chloride, 4~7 parts of magnesium nitrates and 1~3 part of ferric citrate stir evenly, and sterilizing is to get nutrient solution.
5. the preparation method of composite desulfurizing agent according to claim 1, which is characterized in that the step（5）Middle mixed liquor is pressed
Mass ratio 3~5:1, sodium alginate soln is uniformly mixed with polyallylamine to get mixed liquor.
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Application publication date: 20180615 |