CN108926988A - A kind of preparation method of copper-based desulfurizing agent, copper-based desulfurizing agent and preparation system - Google Patents
A kind of preparation method of copper-based desulfurizing agent, copper-based desulfurizing agent and preparation system Download PDFInfo
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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Abstract
The invention belongs to environmental protection and chemical technology fields, disclose the copper-based desulfurizing agent of preparation method and preparation system of a kind of copper-based desulfurizing agent, select Cu2+As active component source, Al3+As carrier source, using hydramine as precipitating reagent, complex hydroxide precipitating is made using coprecipitation, molecular sieve and polyethylene glycol are added as pore creating material, it by ageing after abundant mechanical stirring, washs, drying, it is kneaded and formed to get to the copper-based desulfurizing agent of high-precision that a certain amount of binder is added after roasting grinding composition.The present invention uses alcamines organic base to have pore structure abundant as the desulfurizing agent that precipitating reagent is prepared, this design feature makes its desulfurization precision can reach 10ppb or less, therefore, during ICL for Indirect Coal Liquefaction various chemicals, the desulfurizing agent prevents F- T synthesis noble metal catalyst poisoning aspect in downstream to be of crucial importance in the deep purifying of synthesis gas.
Description
Technical field
The invention belongs to environmental protection and chemical technology field more particularly to a kind of preparation methods of copper-based desulfurizing agent, copper-based de-
Sulphur agent and preparation system.
Background technique
Currently, the prior art commonly used in the trade is such that
Chinese energy mineral resources are at present in reserves composition, coal accounts for 90% or more, and oil gas is less than 10%, with energy
The continuous adjustment of source consumption structure, Demand of Oil & Gas accounting increases, growing with the energy resources structural support less than 10%
Energy consumption structure, it is both dangerous or unsustainable.
Therefore, developing coal liquefaction product and clean fuel using technology is to solve the necessarily choosing of China's oil energy shortage
It selects.Coal liquefaction is to obtain the process of oil product under the effect of the catalyst using coal as raw material, mainly includes direct liquefaction, indirect
Liquefy two kinds of techniques；The direct liquefaction method of coal is exactly using coal as raw material, and direct liquefaction is at hydrocarbon under high-temperature and high-pressure conditions
Object, then the product oils such as gasoline, diesel oil, other fuel oil are produced by rectifying；ICL for Indirect Coal Liquefaction is exactly that coal is raw by gasification furnace
At gasification gas be converted to synthesis gas, and be basic raw material with synthesis gas, hydrocarbon compound be converted into using Fischer-Tropsch Synthesis, and
Liquid fuel and various chemicals are produced by rectifying.The gasification of synthesis gas is prepared in raw materials such as coal, heavy oil, coke
In, the form that S element is eventually converted to hydrogen sulfide is transferred in synthesis gas, and downstream fischer-tropsch synthetic catalyst is caused to be poisoned, very
To inactivation, subsequent product purity is reduced.Therefore need to carry out synthesis gas deep purifying to meet next step process or device pair
The requirement of impurity.Relative to the index of constant temperature fine desulfurizing (low-temp methanol is washed) 0.1ppm, deep purifying index is 10ppb, synthesis
Gas is after deep purifying, and downstream catalyst sulfur poisoning problem is largely alleviated, and service life greatly improves.
Patent document CN101590358A discloses one kind and vulcanizes in chemical fertilizer industry synthesis gas under medium temperature condition for removing
The preparation method of the adsorbent of hydrogen, the method are mediated after mixing soluble ferrite with calcium hydroxide and binder, extrusion at
Type roasts after drying and medium temperature ferric oxide desulfurizer is made.
Patent document CN105013444A discloses a kind of preparation method of solid desulfurating agent, this desulfurizing agent is by 20% 3
Ethanol amine, 10% calcium carbonate, 10% iron hydroxide, 20% ammonium carbonate, 20% carbonic acid aniline, 20%2- ethyltoluene diamines these
Effective component is mixed with aluminium oxide according to 1:1, and is added obtained by binder mixing, which is used for during cracking c_5
The removing of sulfide.Above two method is referred to as blending method, and defect existing for this method is mainly: it is equal that raw material is not easy mixing
Even, active component dispersion degree is not high, the final desulfurization effect for influencing desulfurizing agent.
Patent offers CN103468338 A and discloses a kind of constant temperature fine desulfurizing method of low sulfur-containing gas, by low sulfur-bearing day
Right gas is from top to bottom successively through the peroxide of iron and modified activated carbon, natural gas after obtaining fine de-sulfur, and the active-carbon finely of use is de-
Sulphur agent is one or both of load copper nitrate, nickel nitrate, manganese nitrate and zinc nitrate using active carbon as carrier, so that by
The hydrogen sulfide tail gas levels of processing are less than 0.1ppm.
Patent document CN107008221 A discloses a kind of preparation method of fine de-sulfur antichlor, mainly by silica
Carrier is made, preparation method with silica silica-gel carrier dip loading copper nitrate as main component or copper acetate and hydramine
Simply.
104492247 A of patent document CN discloses a kind of preparation method of obtained magnetic ball desulfurizing agent of infusion process, first by magnetic
Ball carries out a series of pre-treatments to obtain the carrier with high-intensitive high-ratio surface, after magnetic ball heating in vacuum is impregnated in active group
In point solution, it is uniformly dispersed and desulfurizing agent of good performance.
Patent document CN 101590395A discloses a kind of for removing the system of the load-type desulfurizer of sulfide in oil product
Preparation Method, with the molecular sieve after 120-350 DEG C of activation, active carbon and aluminum oxide are that carrier is first impregnated in iron, copper
In equal soluble salt solutions, after be impregnated in inorganic caustic solutions again by drying, filter, dry, roasting obtains product.It should
Defect existing for method is mainly: the solubility of solute is restricted in aqueous solution, and the power that solution immerses in duct is to carry
Inside and outside surface concentration is poor, and active component is loaded on carrier by way of capillary phenomenon and diffusion, therefore active metal
It will receive limitation in the load capacity of the inner surface of carrier, it is undesirable so as to cause desulfurization effect.
Patent document CN104437073 A is related to a kind of preparation method of gas deep purifying compound iron zinc desulfurizing agent,
By ferrous sulfate heptahydrate and lime stone, deionized water hybrid reaction dry, pulverize obtained iron oxidation mixture, while by alkali
Formula zinc carbonate is roasted to activated zinc oxide, after obtained two oxides be mixed to get required compound iron zinc essence with auxiliary agent take off
Sulphur agent.
Patent document CN106179328A discloses a kind of preparation method of deep purifying desulfurizing agent, by zinc nitrate and oxygen
Change aluminium powder and be made into cocurrent after aqueous solution respectively stirred tank is added and be concentrated into slurry, pressure filtration washing at being dried after filter cake, by
Roasting is crossed, powder is ground into and metal oxide powder mixes, add molten made of alkali metal hydroxide or carbonate
Liquid, rear extruded moulding, dry that deep purifying desulfurizing agent is made after mixing evenly.The desulfurizing agent can be by low-temp methanol washing process
H2S is removed to less than 5ppb in the synthesis gas of outlet, protects downstream methanol synthesis, methanation, the catalyst such as F- T synthesis.
Patent document CN101343571 A discloses a kind of preparation method of nano composite oxide meso-porous desulfurizer, to
Ammonium hydroxide is added in manganese nitrate and zirconium nitrate mixed solution to obtain being co-precipitated after solution with after mesoporous material mixing, ultrasound is taken out
It filters dry roasting and metal composite oxide meso-porous desulfurizer is made.It obtains nano particle and is mainly distributed on outer surface, desulfurizing agent
Property is more stable.The above several method be by the way that desulfurizing agent will be obtained with auxiliary agent mixed-forming after active ingredient precipitation and drying,
It is not complete enough that this method has a defect that auxiliary agent disperses with active component；And technique is cumbersome, takes a long time.
In conclusion problem of the existing technology is:
(1) it is generally precipitated in the prior art using inorganic base, since due to by inorganic alkali solubility, precipitating reagent can
Selective alkali type is less, inorganic base such as sodium carbonate, and the alkalinity such as sodium hydroxide is stronger, during precipitation reaction, pH range
Controllability and controllability be restricted, react it is more violent.
(2) prior art is somebody's turn to do by will obtain desulfurizing agent with auxiliary agent mixed-forming after active ingredient precipitation and drying
Method has a defect that auxiliary agent and active group by mechanical mixture, and part material is still within graininess point in mixed process
It dissipates not enough completely；Therefore raw material mixing is not uniform enough in mixed process, and active component dispersion degree is not high, final to influence desulfurization effect
Fruit.
(3) in the prior art there are also catalyst is made using infusion process, this method is had a defect that in dipping process
Active component can not sufficiently achieve the inner surface of carrier, and the higher active component of concentration can influence activity in outer surface aggregation
The diffusion of component inner surface, and the solution where active component can not will cause a large amount of material wave completely by carrier absorption
Take.
(4) it needs to carry out Roasting Decomposition temperature to salt in the prior art to be up to 600 DEG C or more, causes a large amount of energy consumptions；
And roasting generates some sour gas, will form acid rain in the environment, brings larger pollution to environment.
Solve the difficulty and meaning of above-mentioned technical problem:
Invention is used as precipitating reagent using organic amine to solve the above problems, can be since organic amine is with larger solubility
Inventory is increased in unit time, improves reaction efficiency；And organic amine slowly ionizes in the solution as weak base, keeps precipitating orderly
It carries out, reaction is more slow and reaction condition is more mild, in this way can be by active component and support dispersion to molecule rank, more preferably
Guarantee active component dispersion so that active component utilization rate, which reaches, does bigization.Organic amine is made using the structure of organic amine
To can also be used as dispersing agent and template while precipitating reagent, this is to produce with abundant pore structure and have compared with Gao Bibiao
The desulfurizing agent in face provides structural support.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of copper-based desulfurizing agents of preparation method of copper-based desulfurizing agent
And preparation system.The present invention is generated without filtering and washing process, no exhaust gas and waste water, production public good environmental protection.
The invention is realized in this way a kind of preparation method of copper-based desulfurizing agent, a kind of preparation method of copper-based desulfurizing agent,
Select Cu2+As active component source, Al3+As carrier source, using hydramine as precipitating reagent, it is made compound using coprecipitation
Hydroxide precipitating；
Molecular sieve and polyethylene glycol are added as pore creating material, by ageing after stirring, is washed, drying, roasting is ground into
It is kneaded and formed that a certain amount of binder is added after powder, obtains the copper-based desulfurizing agent of high-precision.
Further, the preparation method of the copper-based desulfurizing agent specifically includes:
Step 1 selects Cu2+As the source of active component, being added relative to main active component ratio is that mass fraction is
The mixed solution that one of 30%~70% Metal aluminum salt or any several soluble-salts are configured to, with organic amine such as alcohol
Amine, polyamines polyene control pH as precipitating reagent under conditions of heating water bath, mechanical stirring, are obtained using the method for co-precipitation
Complex hydroxide sediment A；
Gained composite colloid A is aged to stable state under step 1 reaction condition, 1~10% is added afterwards by step 2
Molecular sieve is as duct auxiliary agent, and 1~10% polyethylene glycol is as dispersing agent, heated mechanical mixer after water bath sonicator, and 8 < pH of control <
11, obtain mixed sediment B；
Step 3 will obtain mixed sediment B through centrifuge washing, dry at being 80~120 DEG C in temperature, through Muffle furnace
400~700 DEG C roasting, after be ground into powder of the partial size less than 200 mesh, a certain amount of binder and other auxiliary agents are added to increase
Reinforcement degree, it is kneaded and formed under 30~60% damp condition after mixing, after by being dried at 80~120 DEG C, then through horse
It is not roasted for 400~700 DEG C of furnace, copper-based desulfurizing agent is made.
Further, in step 1, Cu2+Active component source is one of copper chloride, copper nitrate, copper sulphate, copper acetate
Or it is several, mantoquita mass concentration is 5%~25%；
Carrier metal aluminium salt source is aluminum soluble salt, mainly includes one of aluminium chloride, aluminum nitrate, aluminum sulfate or several
The mixture of kind, aluminium salt mass concentration are 3%~20%.
Further, in step 1, organic amine precipitation agent be hydramine (MEA, DEA, TEA, MDEA), enamine (DETA, TETA,
TEPA) any one or a few the mixture in organic amine, preferably DEA, MEA, DETA, TETA, concentration are 5~30%.
Further, water bath heating temperature described in step 1 be 20~100 DEG C, preferably 30~80 DEG C, mechanical stirring speed
For 200~600r/min, be added dropwise the dropwise addition mode of salt using alkali, it is saline and alkaline than being 1:1.2~2, rate of addition control for 1~3 drop/
S, time for adding control in 1~2h, are added dropwise and continue 0.5~1h of stirring.
Further, composite colloid A aging condition is identical as step 1 reaction condition in step 2, and molecular sieve is mainly selected
4X, 5X and 13X, polyethylene glycol select polyethylene glycol 200 or polyethylene glycol 400, and digestion time is 18~36h, heating water bath temperature
Degree is 20~100 DEG C, and preferably 30~80 DEG C, mechanical stirring speed is 200~600r/min.
Further, centrifugal washing times described in step 3 are to wash three times, and alcohol is washed three times.The binder is swelling
One or more of soil, kaolin, additional amount accounts for the 1~30% of sample.
Another object of the present invention is to provide a kind of copper-based desulfurizing agents of the preparation method preparation of copper-based desulfurizing agent.
Another object of the present invention is to provide a kind of copper-based desulfurizing agents of preparation method using the copper-based desulfurizing agent
Preparation system.
Another object of the present invention is to provide a kind of coal liquid prepared by the preparation method using the copper-based desulfurizing agent
Change clean fuel.
Above-mentioned prepared molding copper oxide desulfurizing agent removing precision can reach 10ppb hereinafter, removing capacity is up to
14.75%, specific surface is in 20~70m2Between/g, pore volume is in 0.58cm3/ g or more, average pore size between 6~15nm,
70% or more is all mesoporous.
In conclusion advantages of the present invention and good effect are as follows:
Copper-based desulfurizing agent prepared by the present invention is under middle cryogenic conditions to H2S adsorption rate is high, and stability is relatively stable；Tail
Gas detects H2S content is always maintained at 10ppb, and adsorbs Sulfur capacity and can reach 14.75%.It is main living that the following are one kind with copper oxide
The gas deep purifying copper oxide desulfurizing agent of property component.
The present invention is used as precipitating reagent and template using organic amine, and comparison sodium hydroxide, sodium carbonate, sodium bicarbonate etc. is inorganic
Alkali has the advantage that
(1) organic amine belongs to weak base so that reaction system pH condition is milder, and in aqueous solution slowly after ionization with gold
Belong to reactant salt, so that precipitation reaction carries out orderly, effectively having evaded the mistake of the system as caused by rate of addition and concentration of lye
Difference and human error.
(2) organic amine wiring solution-forming point, which is added dropwise to, has fully ensured that aluminium salt and mantoquita react generation hydroxide with organic amine
Dispersibility, so that active component is evenly distributed in the inside and surface of carrier, so that active component be made in final product to aoxidize
The utilization rate of copper maximizes.
(3) organic amine plays multiple action in the reaction, is both precipitating reagent and dispersing agent or template, this is
Prepare flourishing cellular structure, higher specific surface, relatively narrow pore-size distribution, high degree of dispersion the desulfurizing agent in activated centre mention
For basis.
The method that the present invention uses ultrasonic water bath, at a certain temperature with dispersing agent by gained precipitating after ageing and pore creating material
By water bath with thermostatic control ultrasound, so that obtained desulfurizing agent presoma has pore structure abundant and good dispersion performance.
Solid desulfurating agent itself small toxicity that the preparation method of copper-based desulfurizing agent provided by the invention is produced, property are steady
It is fixed, it is not volatile, it is nonflammable, people's life security can be effectively ensured.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of copper-based desulfurizing agent provided in an embodiment of the present invention.
Fig. 2 is the preparation system schematic diagram of copper-based desulfurizing agent provided in an embodiment of the present invention.
Fig. 3 is that the BET isothermal of desulfurizing agent provided in an embodiment of the present invention inhales (de-) attached curve graph；
Fig. 4 is desulfurizing agent BJH method pore size distribution curve figure provided in an embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The preparation method of Fig. 1, copper-based desulfurizing agent provided in an embodiment of the present invention includes:
S101: selection Cu2+As the source of active component, being added relative to main active component ratio is that mass fraction is
The mixed solution that one of 30%~70% Metal aluminum salt or any several soluble-salts are configured to, with organic amine such as alcohol
Amine, polyamines polyene control pH as precipitating reagent under conditions of heating water bath, mechanical stirring, are obtained using the method for co-precipitation
Complex hydroxide sediment A；
S102: gained composite colloid A is aged to stable state, 1~10% molecular sieve is added afterwards as duct auxiliary agent, and 1
As dispersing agent, heated mechanical mixer after water bath sonicator controls 8 < pH < 11, obtains mixed sediment B~10% polyethylene glycol；
S103: mixed sediment B will be obtained through centrifuge washing, dried at being 80~120 DEG C in temperature, through Muffle furnace 400
~700 DEG C roasting, after be ground into powder of the partial size less than 200 mesh, a certain amount of binder and other auxiliary agents are added to increase
Intensity, it is kneaded and formed under 30~60% damp condition after mixing, after by being dried at 80~120 DEG C, then through Muffle
400~700 DEG C of furnace are roasted, and copper-based desulfurizing agent is made
The invention will be further described combined with specific embodiments below.
Embodiment 1
1. weighing the AlCl of 0.04mol3.6H2Cu (the NO of O, 0.08mol3)2, it is configured to Cu (NO3)2Mass fraction is
10% solution A is poured into 500mL three-necked flask, spare.
2. weigh 0.121mol diethylenetriamine (EDTA) again, the lye B for being configured to that mass fraction is 10% is spare.
3. Cu (NO will be equipped with3)2The three-necked flask of solution A is placed in 70 DEG C of water-bath, is opened stirring 400r/min, is used
Lye B to Cu (NO is added dropwise in constant pressure funnel3)2In solution A, time for adding control controls 8 < pH < 10 in 1.5h or so；
4. stopping reaction after being added dropwise to complete subsequent continuous insulated and stirred 1h, the precipitating of acquisition is placed under reaction temperature and is aged
18h。
5. completion to be aged, the rear 5%13X molecular sieve that is added as duct auxiliary agent, 5% polyethylene glycol as dispersing agent,
Gained sediment, is used ethyl alcohol and deionized water centrifuge washing three times by ultrasound 1h under the conditions of 70 DEG C of water-bath respectively, and 7 < pH of holding <
10, it is centrifugally separating to obtain compound alumine hydroxide colloid C.
6. the composite colloids C after washing is placed in 85 DEG C of baking oven drying, composite hydrous oxide D is obtained；
7. by composite hydrous oxide D pass through 600 DEG C of roasting 2h of Muffle furnace, after be ground into powder of the partial size less than 200 mesh,
Obtain desulfurizing agent original powder S.
8. weighing 20g desulfurizing agent original powder, the bentonite adhesive of 2g is added, is pinched under 40% damp condition after mixing
Synthesis type, after by drying at 120 DEG C, then through 600 DEG C of Muffle furnace roastings obtain composite oxide desulfurizing agent SA。
Embodiment 2
1. weighing the AlCl of 0.06mol3.6H2Cu (the NO of O, 0.08mol3)2, it is configured to Cu (NO3)2Mass fraction is
10% solution A is poured into 500mL three-necked flask, spare
2. weigh 0.147mol diethylenetriamine (EDTA) again, the lye B for being configured to that mass fraction is 10% is spare.
3. Cu (NO will be equipped with3)2The three-necked flask of solution A is placed in 70 DEG C of water-bath, is opened stirring 400r/min, is used
Lye B to Cu (NO is added dropwise in constant pressure funnel3)2In solution A, time for adding control controls 8 < pH < 10 in 1.5h or so；
4. stopping reaction after being added dropwise to complete subsequent continuous insulated and stirred 1h, the precipitating of acquisition is placed under reaction temperature by acquisition
It is aged 18h.
5. completion to be aged, the rear 5%13X molecular sieve that is added as duct auxiliary agent, 5% polyethylene glycol as dispersing agent,
Gained sediment, is used ethyl alcohol and deionized water centrifuge washing three times by ultrasound 1h under the conditions of 70 DEG C of water-bath respectively, and 7 < PH of holding <
10, it is centrifugally separating to obtain compound alumine hydroxide colloid C.
6. the composite colloids C after washing is placed in 85 DEG C of baking oven drying, composite hydrous oxide D is obtained；
7. by composite hydrous oxide D pass through 600 DEG C of roasting 2h of Muffle furnace, after be ground into powder of the partial size less than 200 mesh,
Obtain desulfurizing agent original powder S.
8. weighing 20g desulfurizing agent original powder, the bentonite adhesive of 2g is added, is pinched under 40% damp condition after mixing
Synthesis type, after by drying at 120 DEG C, then through 600 DEG C of Muffle furnace roastings obtain composite oxide desulfurizing agent SB。
Embodiment 3
1. weighing the AlCl of 0.08mol3.6H2Cu (the NO of O, 0.08mol3)2, it is configured to Cu (NO3)2Mass fraction is
10% solution A is poured into 500mL three-necked flask, spare.
2. weigh 0.173mol diethylenetriamine (EDTA), the lye B for being configured to that mass fraction is 10% is spare.
3. Cu (NO will be equipped with3)2The three-necked flask of solution A is placed in 70 DEG C of water-bath, is stirred 400r/min, is used constant pressure
Lye B to Cu (NO is added dropwise in dropping funel3)2In solution A, time for adding control controls 8 < pH < 10 in 1.5h or so；
4. stopping reaction after being added dropwise to complete subsequent continuous insulated and stirred 1h, the precipitating of acquisition is placed under reaction temperature and is aged
18h。
5. 5%13X molecular sieve is added after the completion of to be aged as duct auxiliary agent, 5% polyethylene glycol is as dispersing agent, in water
Gained sediment, is used ethyl alcohol and deionized water centrifuge washing three times by ultrasound 1h under the conditions of 70 DEG C of bath respectively, keeps 7 < pH < 10,
It is centrifugally separating to obtain compound alumine hydroxide colloid C.
6. the composite colloids C after washing is placed in 85 DEG C of baking oven drying, composite hydrous oxide D is obtained；
7. by composite hydrous oxide D pass through 600 DEG C of roasting 2h of Muffle furnace, after be ground into powder of the partial size less than 200 mesh,
Obtain desulfurizing agent original powder S.
8. weighing 20g desulfurizing agent original powder, the bentonite adhesive of 2g is added, is pinched under 40% damp condition after mixing
Synthesis type, after by drying at 120 DEG C, then through 600 DEG C of Muffle furnace roastings obtain composite oxide desulfurizing agent SC。
Embodiment 4
1. weighing the AlCl of 0.12mol3.6H2Cu (the NO of O, 0.08mol3)2, it is configured to Cu (NO3)2Mass fraction is
10% solution A is poured into 500mL three-necked flask, spare.
2. weigh 0.225mol diethylenetriamine (DEA) again, the lye B for being configured to that mass fraction is 10% is spare.
3. Cu (NO will be equipped with3)2The three-necked flask of solution A is placed in 70 DEG C of water-bath, is stirred 400r/min, is used constant pressure
Lye B to Cu (NO is added dropwise in dropping funel3)2In solution A, time for adding control controls 8 < pH < 10 in 1.5h or so；
4. stopping reaction after being added dropwise to complete subsequent continuous insulated and stirred 1h, the precipitating of acquisition is placed under reaction temperature and is aged
18h。
5. completion to be aged, the rear 5%13X molecular sieve that is added as duct auxiliary agent, 5% polyethylene glycol as dispersing agent,
Gained sediment, is used ethyl alcohol and deionized water centrifuge washing three times by ultrasound 1h under the conditions of 70 DEG C of water-bath respectively, and 7 < pH of holding <
10, it is centrifugally separating to obtain compound alumine hydroxide colloid C.
6. the composite colloids C after washing is placed in 85 DEG C of baking oven drying, composite hydrous oxide D is obtained；
7. by composite hydrous oxide D pass through 600 DEG C of roasting 2h of Muffle furnace, after be ground into powder of the partial size less than 200 mesh,
Obtain desulfurizing agent original powder S.
8. weighing 20g desulfurizing agent original powder, the bentonite adhesive of 2g is added, is pinched under 40% damp condition after mixing
Synthesis type, after by drying at 120 DEG C, then through 600 DEG C of Muffle furnace roastings obtain composite oxide desulfurizing agent SD。
Below with reference to activity rating example, the invention will be further described.
Activity rating example:
Desulfurization performance test is carried out to the copper oxide desulfurizing agent that specific example 1~4 above-mentioned in the present invention is prepared.
In this test, evaluation unstripped gas (H2S/N2) import hydrogen sulfide content control in 6000-8000ppm or so, air speed
400-1000h-1, 100 DEG C of desulfurization environment temperature.Desulfurizing agent obtained is smashed and is sieved, the little particle of 16-40 mesh is obtained, according to
Certain regular uniform is fitted into homemade fixed-bed micro-reactor, and the upper and lower are respectively charged into quartz sand and fix, control catalysis
Agent bed ratio of height to diameter is 5~8.
Fig. 2 is the preparation system of copper-based desulfurizing agent provided in an embodiment of the present invention.For into and out of in implication in evaluation procedure
H2The analysis of S content is analyzed using mercurimetry.Reactor tail gas is detected with the dedicated chromatography TY-2000 of gas micro-analysis
Mouth hydrogen sulfide content, detection are limited to 5ppb.By to inlet and outlet hydrogen sulfide content CInto、COut, the real-time air speed S of unstripped gasy, sulphur absorb
The measurement of the parameters such as time t, desulfurizing agent bed layer heap density d, carrys out the desulfurization performance of overall merit ferric oxide desulfurizer.Work as reactor
Just start to detect the H of 10ppb in tail gas2When S, default desulfurizing agent has been inactivated, and Sulfur capacity at this time is referred to as working sulfur capacity, sulphur
Hold size to be calculated by following formula:
Wherein, S --- working sulfur capacity；
ms--- the quality of Catalyst Adsorption sulfide in experimentation；
The quality of M --- loading catalyst；
CInto、COut--- experimental provision imports and exports sulfide content g/m3；
Sy--- experimentation gas space velocity, h-1；
T --- the time required to experiment penetrates, h；
D --- catalyst bulk density g/ml.
Under the test conditions above, copper oxide desulfurizing agent S example 1-4 being preparedA-DUnder Fig. 2 evaluation rubric
Its desulfurization performance is evaluated, test result is as shown in table 1:
1 example 1-4 copper oxide desulfurizing agent S of tableA-DEvaluation result
It can using the copper-based desulfurizing agent highest penetration capacity of the preparation in the present invention it can be seen from 1 test result of table
To reach 14.75%.
For the internal pore structure situation for really reflecting desulfurizing agent, JW-BK112 type N2 adsorption specific surface and pore analysis are used
Instrument tests the pore structure of obtained desulfurizing agent, and test result is as shown in table 2:
2 example of table, 1~4 copper oxide desulfurizing agent SA-DPore structure analysis result
Using the de- of the preparation method preparation of the copper oxide desulfurizing agent in the present invention it can be seen from 2 test result of table
Sulphur agent specific surface is in 20~70m2Between/g, pore volume is in 0.58cm3/ g or more, average pore size is between 6~15nm, and 70%
Above be all it is mesoporous, contain a small amount of macropore and minimal amount of micropore.Meanwhile (de-) is inhaled in conjunction with the isothermal of 3 desulfurizing agent of attached drawing
The desulfurizing agent pore size distribution curve of attached curve and attached drawing 4, can from which further follow that, prepared copper oxide desulfurizing agent is average
Sulfur capacity highest when aperture is 15.67nm, this is because the characterization of pore size is diffusion feelings of the hydrogen sulfide gas inside particle
Condition can guarantee that shape enters inside catalyst pores for the gas cure hydrogen molecule of V-type when aperture is larger in a certain range, and
And it can be freely accessible to catalytic inner after hydrogen sulfide reacts generation copper sulfide with the copper oxide on surface, with desulfurizer activity group
Divide sufficiently reaction.
Sample S will be obtained with infusion process under the test conditions aboveE, sample S that blending method obtainsF, sample is obtained with the present invention
Product SBHDS evaluation is carried out, evaluation result is obtained and is as follows:
3 copper oxide desulfurizing agent S of tableB,SE-FEvaluation result
The desulfurizing agent prepared it can be seen from 3 test result of table with currently available technology on Sulfur capacity be respectively
10.17% and 14.63% not departing from 14.75% Sulfur capacity of the invention, and on desulfurization precision relatively far apart, infusion process
Tail gas detection level still has 50ppb after gained desulfurizing agent removing H2S, and desulfurizing agent H2S tail gas made from blending method is up to
200ppb does not meet requirement of the series reactions such as downstream F- T synthesis to synthesis gas even more.So desulfurization provided by the invention
The desulfurizing agent that agent preparation method is prepared all has preferable superiority on desulfurization precision and Sulfur capacity.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of copper-based desulfurizing agent, which is characterized in that the preparation method of the copper-based desulfurizing agent selects Cu2+As
Active component source, Al3+As carrier source, using hydramine as precipitating reagent, complex hydroxide precipitating is made using coprecipitation；
Molecular sieve and polyethylene glycol are added as pore creating material, by ageing after stirring, is washed, drying, after roasting is pulverized
It is kneaded and formed that a certain amount of binder is added, obtains the copper-based desulfurizing agent of high-precision.
2. the preparation method of copper-based desulfurizing agent as described in claim 1, which is characterized in that the preparation side of the copper-based desulfurizing agent
Method specifically includes:
Step 1 selects Cu2+As the source of active component, it is 30% that addition, which is mass fraction relative to main active component ratio,
The mixed solution that one of~70% Metal aluminum salt or any several soluble-salts are configured to is more with organic amine such as hydramine
Alkene polyamines controls pH as precipitating reagent under conditions of heating water bath, mechanical stirring, obtains compound hydrogen using the method for co-precipitation
Oxide precipitation object A；
Gained composite colloid A is aged to stable state under step 1 reaction condition, 1~10% molecule is added afterwards by step 2
Sieve is used as duct auxiliary agent, and 1~10% polyethylene glycol is used as dispersing agent, heated mechanical mixer after water bath sonicator, control 8 < pH < 11,
Obtain mixed sediment B；
Step 3 will obtain mixed sediment B through centrifuge washing, dry at being 80~120 DEG C in temperature, through Muffle furnace 400~
700 DEG C of roastings, after be ground into powder of the partial size less than 200 mesh, it is strong to increase that a certain amount of binder and other auxiliary agents are added
Degree, it is kneaded and formed under 30~60% damp condition after mixing, after by being dried at 80~120 DEG C, then through Muffle furnace
400~700 DEG C are roasted, and copper-based desulfurizing agent is made.
3. the preparation method of copper-based desulfurizing agent as claimed in claim 2, which is characterized in that
In step 1, Cu2+Active component source is one or more of copper chloride, copper nitrate, copper sulphate, copper acetate, mantoquita
Mass concentration is 5%~25%；
Carrier metal aluminium salt source is aluminum soluble salt, mainly including one or more of aluminium chloride, aluminum nitrate, aluminum sulfate
Mixture, aluminium salt mass concentration are 3%~20%.
4. the preparation method of copper-based desulfurizing agent as claimed in claim 2, which is characterized in that
In step 1, organic amine precipitation agent is hydramine, any one or a few the mixture in enamine organic amine, concentration 5
~30%.
5. the preparation method of copper-based desulfurizing agent as claimed in claim 2, which is characterized in that heating water bath temperature described in step 1
Degree is 20~100 DEG C, mechanical stirring speed is 200~600r/min, and the dropwise addition mode of salt is added dropwise using alkali, saline and alkaline than being 1:
1.2~2, rate of addition control is 1~3 drop/S, and time for adding controls in 1~2h, is added dropwise and continues 0.5~1h of stirring.
6. the preparation method of copper-based desulfurizing agent as claimed in claim 2, which is characterized in that composite colloid A is aged in step 2
Condition is identical as step 1 reaction condition, and molecular sieve mainly selects 4X, 5X and 13X, and polyethylene glycol selects polyethylene glycol 200 or poly-
Ethylene glycol 400, digestion time are 18~36h, and water bath heating temperature is 20~100 DEG C, and mechanical stirring speed is 200~600r/
min。
7. the preparation method of copper-based desulfurizing agent as claimed in claim 2, which is characterized in that centrifuge washing described in step 3
Number is washes three times, and alcohol is washed three times.The binder is one or more of bentonite, kaolin, and additional amount accounts for the 1 of sample
~30%.
8. a kind of copper-based desulfurizing agent of the preparation method preparation of copper-based desulfurizing agent as described in claim 1.
9. a kind of preparation system of the copper-based desulfurizing agent using the preparation method of copper-based desulfurizing agent described in claim 1.
10. a kind of coal liquefaction clean fuel prepared by the preparation method using copper-based desulfurizing agent described in claim 1.
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| CN115945058A (en) * | 2023-03-14 | 2023-04-11 | 山东中科纯净环保科技有限公司 | Calcium hydroxide strip-shaped desulfurizer and preparation method thereof |
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| CN115945058A (en) * | 2023-03-14 | 2023-04-11 | 山东中科纯净环保科技有限公司 | Calcium hydroxide strip-shaped desulfurizer and preparation method thereof |
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Application publication date: 20181204 |