CN107596904B - A kind of high sulfur capacity zinc oxide fine desulfurizer and preparation method thereof - Google Patents
A kind of high sulfur capacity zinc oxide fine desulfurizer and preparation method thereof Download PDFInfo
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- CN107596904B CN107596904B CN201711097581.5A CN201711097581A CN107596904B CN 107596904 B CN107596904 B CN 107596904B CN 201711097581 A CN201711097581 A CN 201711097581A CN 107596904 B CN107596904 B CN 107596904B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 54
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000011593 sulfur Substances 0.000 title claims abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 70
- 239000002994 raw material Substances 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 42
- 238000004898 kneading Methods 0.000 claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 23
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000000853 adhesive Substances 0.000 claims abstract description 10
- 230000001070 adhesive effect Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 24
- 239000003595 mist Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000012216 screening Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011265 semifinished product Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000004568 cement Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229920001206 natural gum Polymers 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 45
- 230000003009 desulfurizing effect Effects 0.000 abstract description 35
- 238000006477 desulfuration reaction Methods 0.000 abstract description 15
- 230000023556 desulfurization Effects 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- -1 extrusion aid Substances 0.000 abstract description 5
- 239000000314 lubricant Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000000428 dust Substances 0.000 description 7
- 238000010348 incorporation Methods 0.000 description 7
- 230000001404 mediated effect Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000005414 inactive ingredient Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- IBBSHLLCYYCDGD-UHFFFAOYSA-N helium mercury Chemical compound [He].[Hg] IBBSHLLCYYCDGD-UHFFFAOYSA-N 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treating Waste Gases (AREA)
Abstract
The present invention relates to a kind of high sulfur capacity zinc oxide fine desulfurizers, and by weight, raw material composition includes 28 parts of 90 98 parts of active oxidation zinc powder and adhesive, and the activated zinc oxide powder includes activated zinc oxide powders A and active oxidation zinc powder B；Wherein, activated zinc oxide powders A accounts for the 92 98% of active oxidation zinc powder gross mass, and zinc oxide content is 92 95%, and heap density is 0.25 0.40kg/l；Active oxidation zinc powder B accounts for the 2 8% of active oxidation zinc powder gross mass, and zinc oxide content is 85 90%, and heap density is 0.10 0.25kg/l.The present invention solve in existing kneading method because raw material mixing be not easy uniformly due to caused by desulfurizing agent processing, properity is undesirable or defective the problems such as.Desulfurizing agent of the present invention includes only two kinds of components, addition auxiliary agent, pore creating material, extrusion aid, lubricant is not necessary in preparation process, the content of activated zinc oxide is high, and active sites are more and dispersion degree is big, and desulfurization effect is good, the H under certain working condition2S working sulfur capacities are up to 30% or more, desulfurization precision≤0.03ppm.
Description
Technical field
The present invention relates to a kind of high sulfur capacity zinc oxide fine desulfurizers and preparation method thereof, belong to gas purification technique field.
Background technology
Desulfurizing agent is used to remove the free sulphur or sulfide in fuel, raw material or gas material, in petrochemical industry, coalification
The industries such as work, chemical fertilizer, environmental protection are got a lot of applications.Desulfurizing agent product category is more in the prior art, by its contained activearm
Activated carbon desulphurization agent, molecular sieve desulfurizer, manganese oxide desulfurizing agent, ferric oxide desulfurizer and Zinc oxide desulfurizer etc. can be divided by dividing.
Compared with above-mentioned various desulfurizing agents, Zinc oxide desulfurizer has desulfurization effect good, stable, right using simplicity, performance
The features such as requirement of process conditions is more relaxed.The preparation method of Zinc oxide desulfurizer is broadly divided into two kinds：The precipitation method and kneading
Method.
The technological process of the precipitation method can be briefly described below：Zinc solution and precipitating reagent (generally carbonate or hydroxide
Object) reaction generates zinc carbonate or zinc hydroxide precipitation, sediment is washed, filtering, after dry, roasting again with auxiliary agent, binder,
The other components such as pore creating material are mediated, be dried again after kneaded material extruded moulding, roast just desulfurizing agent finished product, Chinese patent
CN201410356116.9, CN201410559638.9, CN201610154640.7 and United States Patent (USP) US9421516B2 are all made of
This method prepares Zinc oxide desulfurizer.Although precipitation method technology maturation, there are following deficiencies：(1) not energy-efficient：In production process
It needs to consume a large amount of thermal energy and electric energy；(2) not environmentally：It will produce a large amount of waste water in production process；(3) uneconomical：Equipment
Investment and maintenance cost are high；(4) not efficiently：The technological process of production is long, more using equipment, and cumbersome.
Kneading method belongs to a kind of solid reaction process, active component (or its presoma) zinc oxide or carbon of Zinc oxide desulfurizer
Sour zinc, auxiliary agent, binder, pore creating material etc. are mixed in kolleroang by physical action, are mediated, and kneaded material is through extrusion, drying, roasting
It burns and just obtains desulfurizing agent finished product.This method preparation process is simple, and investment is small, and low energy consumption, and production process is generated without waste water, both energy-saving ring
It is relatively broad to protect economical and efficient, application again.Chinese patent CN200810113028.0, CN200810113029.5,
CN201010274016.3, CN201110429682.4, CN201510293596.3 and United States Patent (USP) US8314047B2,
US8236262B2, US8702974B2 are all made of this method and prepare Zinc oxide desulfurizer.
Compared with the precipitation method, kneading method have larger advantage, but itself there are still following deficiencies：(1) actual production
In to ensure yield, raw material cannot stop for a long time in kolleroang, and often not enough uniformly, therefore part grain size is consistent for mixing
Or similar feed particles form tight grain group in kneading process, internal void is few, causes desulfurizing agent hole to hold small, to
Reduce the Sulfur capacity and desulfurization precision of desulfurizing agent；(2) after kneading part material powder still under dry state (in kneading process
The water of addition fails to be diffused into the part material powder), and these dry powders extrusion easy to wear during follow-up extrusion
Machine screw rod, influences equipment life.In addition, there is a certain amount of air for the gap between raw material powder, it is empty in extrusion process
Partial air in gap cannot be escaped and stayed in extrudate in time, and when pressure is removed, extrudate inner air will be swollen
It is swollen that extrudate pine is caused to split.
To solve the above problems, technical staff added in the production of Zinc oxide desulfurizer help crowded, pore creating material, help it is crowded
Agent, lubricant etc. (such as Chinese patent CN200810113028.0, CN200810113029.5, CN201110429682.4),
But there are two big defects for this way：First, pore creating material, extrusion aid, lubricant are all inactive ingredients, the type being added
More with quantity, the active component of desulfurizing agent is fewer, and Sulfur capacity is lower；Second is that the surface flatness of different material is generally poor
It is different larger, therefore the type of added raw material is more, the surface binding force between various raw materials is lower, needs binder to be added
It is more, it is reduced so as to cause the active component of desulfurizing agent, Sulfur capacity also accordingly reduces.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of without addition auxiliary agent and a variety of inactive ingredients (i.e. pore-creating
Agent, extrusion aid, lubricant), and the high sulfur capacity zinc oxide fine desulfurizer and preparation method thereof that active component ratio is high, while the party
Method can avoid reducing because raw material mixes the uneven Sulfur capacity for causing desulfurizing agent hole to hold the small desulfurizing agent to caused by and desulfurization precision, be dry
The problem of material extrusion equipment easy to wear and the easy pine of extrudate are split.
In order to solve the above-mentioned technical problem, technical scheme is as follows：A kind of high sulfur capacity zinc oxide fine desulfurizer, is pressed
Parts by weight meter, raw material composition include 2-8 parts of 90-98 parts of active oxidation zinc powder and adhesive, the active oxidation zinc powder
Including activated zinc oxide powders A and active oxidation zinc powder B；
Wherein, activated zinc oxide powders A accounts for the 92-98% of active oxidation zinc powder gross mass, activated zinc oxide powders A
Heap density is 0.25-0.40kg/l, and powder D10 grain sizes are 1.5-3 μm, D50 grain sizes are 6-15 μm, D90 grain sizes are 20-30 μm；
Active oxidation zinc powder B accounts for the 2-8% of active oxidation zinc powder gross mass, the heap density of active oxidation zinc powder B
For 0.10-0.25kg/l, powder D10 grain sizes are 0.5-1.5 μm, D50 grain sizes are 2-5 μm, D90 grain sizes are 7-10 μm.
Preferably, the activated zinc oxide powders A is after being sieved zinc oxide purchased in market with shaking screen by obtaining,
Its zinc oxide content is 92-95wt%.
Preferably, zinc oxide content is 85-90wt% in the active oxidation zinc powder B.
The adhesive is one or more in kaolin, cement, waterglass, clay, dried starch, natural gum.
Preferably, the powder diameter is surveyed by laser particle size analyzer.
In the present invention, powder D10 grain sizes, D50 grain sizes, D90 grain sizes are respectively cumulative distribution in powder size distribution curve
For the equivalent diameter (average diameter) of 10%, 50%, 90% the largest particles.
Based on same inventive concept, the present invention also provides a kind of preparations of high sulfur capacity zinc oxide fine desulfurizer as described above
Method includes the following steps：
S1, activated zinc oxide powders A and active oxidation zinc powder B are weighed according to the ratio, mixed, obtain active oxygen
Change zinc powder；
S2, it will be added in kneading machine together with the mixed active oxidation zinc powders of S1 and adhesive, mix at room temperature,
15-60min is mediated in stirring, suitable water is added in kneading process so that all materials mixture is fully soaked；Wherein, water
Additive amount be material total amount 2-5wt%；
S3, extrusion forming is carried out to the kneading material finally obtained in S2, obtains high sulfur capacity zinc oxide fine desulfurizer crude green body；
S4, the high sulfur capacity zinc oxide fine desulfurizer crude green body obtained in S3 is placed in baking oven, under the conditions of 90-120 DEG C, is dried
Dry 2-4h, obtains high sulfur capacity zinc oxide fine desulfurizer semi-finished product；
S5, the air atmosphere environment that the high sulfur capacity zinc oxide fine desulfurizer semi-finished product obtained in S4 are placed in 450-600 DEG C
Under, 2-5h is roasted, high sulfur capacity zinc oxide fine desulfurizer finished product is obtained.
In S1, mixing rate 3-20r/min, incorporation time 15-60min.
In S1, the mixing of activated zinc oxide powders A and active oxidation zinc powder B is carried out by hopper mixing machine.
In S1, zinc oxide purchased in market is sieved by shaking screen, acquisition heap density is 0.25-0.40kg/l, powder D10
The raw material powder that grain size is 1.5-3 μm, D50 grain sizes are 6-15 μm, D90 grain sizes are 20-30 μm, as activated zinc oxide powders A
It comes into operation.
While S2 is proceeded by, pass through the raw material powder generated when micro mist collection system collection Manual material feeding.Preferably,
Kneading machine enables micro mist collection system immediately after opening.Further, the micro mist collection system by dust hood, dust collecting duct,
Air-introduced machine, air compressor, bag filter, exhaust outlet composition, the dust hood are mounted at kneading machine feeding port, the suction
Dust hood is connect by dust collecting duct with bag filter, and the air-introduced machine is connect by dust collecting duct with bag filter, described
Air compressor is connect by hose with bag filter, and the exhaust outlet is mounted on bag filter.
Further, when collecting raw material powder, pass through the heap density and grain size of the powder that regulating air volume control is collected.
Preferably, air force is controlled by adjusting the electric machine frequency of air-introduced machine, it is preferable that the electric machine frequency is 20-50Hz.
Further, the raw material powder of collection is sieved by shaking screen, acquisition heap density is 0.10-0.25kg/
L, the raw material powder that powder D10 grain sizes are 0.5-1.5 μm, D50 grain sizes are 2-5 μm, D90 grain sizes are 7-10 μm, as active oxygen
Change zinc powder B to come into operation.
Compared with prior art, beneficial effects of the present invention are as follows：
(1) present invention has collected the raw material powder generated when Manual material feeding in desulfurizing agent preparation process using micro mist collection system
Dirt, and it is back to use in production again, workshop dust pollution is reduced from source and realizes the recycling profit of raw material
With reducing the waste of raw material to greatest extent, improve production efficiency.
(2) the preparation elder generation hopper mixing machine of inventive desulfurization agent is by activated zinc oxide powders A and active oxidation zinc powder B
It is mixed by certain mass ratio, applicant has found by a large number of experiments：In set incorporation time, mixing rotating speed and material
Under conditions of proportioning, it is best only to have reached this there are a best particle diameter distribution for mixed raw material (powdered)
Particle diameter distribution, the number or degree that following problems occur are only minimum：Desulfurizing agent hole is caused to hold because raw material mixing is uneven
Small Sulfur capacity and desulfurization precision to cause desulfurizing agent, which reduces, dry material extrusion equipment easy to wear and the easy pine of extrudate are split asks
Topic, full and uniform admixture has been had reached to demonstrate the raw material powder under optimum grain-diameter distribution.This is because
Under best particle diameter distribution state, a certain number of small particle particles have been filled between the hole of big or middle grain size particle, shape
At the optimum agglomerated masses of fine particles of microstructure (binding force, porosity, specific surface area optimum i.e. between particle), will not go out
Now part grain size is consistent or similar feed particles are the phenomenon that kneading process forms tight grain group and after kneading
The problem of part material powder is still in dry state, while small particle particle in the filling process will be in big or middle grain size particle hole
Air squeeze out, avoid the problem of banded extruder extrudate pine is split.
Mixed raw material (powdered) particle diameter distribution can simply be characterized with D10 grain sizes, D50 grain sizes and D90 grain sizes, Shen
The heap density and raw material proportioning of raw material before finding mixed raw material (powdered) particle diameter distribution and mixing of asking someone have very high
Correlation.Therefore, in actual production to improve efficiency, reducing cost, match setting incorporation time, mixing rotating speed and material
Than after, can the mixture homogeneity of raw material directly be controlled by controlling the heap density of raw material, specifically, micro mist collection system is collected
The heap density of raw material powder controlled by two procedures：1) coarse adjustment：The air quantity of air-introduced machine is adjusted, ordinary circumstance downdraft is smaller, receives
The pile of grounds density and grain size of collection are with regard to smaller.And the air quantity of air-introduced machine is controlled by adjusting the electric machine frequency of air-introduced machine；
2) it finely tunes：The raw material powder of collection is sieved using shaking screen, it is spare to sieve qualified raw material powder.The heap of zinc oxide purchased in market is close
Degree is then controlled it by using shaking screen.
In conclusion present invention employs methods reliable, efficient, inexpensive, easy to operate creatively to solve now
There is raw material mixing in kneading method to be not easy uniform problem.The porosity of zinc oxide fine desulfurizer is 0.25-0.45, and specific surface area is
80-100m2/ g (improves 20%-30%) than existing Zinc oxide desulfurizer, accelerates H in gas2Expansions of the S inside desulfurizing agent
It dissipates, improve H2The rate of S and reactive desulfurizing agent substantially increase the Sulfur capacity and desulfurization precision of desulfurizing agent.
(3) desulfurizing agent of the invention includes only two kinds of components --- activated zinc oxide and adhesive, is not necessary in preparation process
Add auxiliary agent, pore creating material, extrusion aid, lubricant.Desulfurizing agent removes H2S is carried out by following reactions：ZnO+H2S=ZnS+
H2The content of O, inventive desulfurization agent activated zinc oxide are very high (reaching as high as 95%), and active sites are more and dispersion degree is high, unit
Volume activity position is higher 10%-20% than existing Zinc oxide desulfurizer.Inventive desulfurization agent removes H2The working sulfur capacity of S is up to 30%
More than, desulfurization precision≤0.03ppm.
(4) material composition of inventive desulfurization agent only has two kinds of active oxidation zinc powder and adhesive, and activated zinc oxide
Powder accounts for the overwhelming majority.Cohesion when kneading between feed particles is big, need to only add a small amount of adhesive and can guarantee desulfurization
The high crush strength (reaching as high as 100N/cm) of agent finished product.
(5) inventive desulfurization agent, since its ingredient overwhelming majority is ZnO tiny crystal grains, substantially will not in high-temperature roasting
There is crystal grain agglomerate and grow up, the phenomenon that lose a part of specific surface area (i.e. sintering), and prior art zinc oxide desulfurization
The preparation of agent often also added other metallic compounds such as copper, these compounds are easy sintering in high-temperature roasting, to lead
Desulfurizing agent Sulfur capacity is caused to decline.
Specific implementation mode
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.
Embodiment 1
The preparation process of desulfurizing agent includes the following steps in the present embodiment：
S1：Zinc oxide purchased in market is sieved by shaking screen, and is the raw material powder of 0.30kg/l by heap density after screening
It collects spare；The raw material powder collected by micro mist collection system (the raw material powder hereinafter referred to as collected) is sieved by shaking screen
Point, and the raw material powder collection that heap density after screening is 0.16kg/l is spare；
S2：Zinc oxide purchased in market after the screening of the 94 parts by weight raw material powder spare with the collection of 2.5 parts by weight is added to
It is mixed in hopper mixing machine, mixing rotating speed is 10rpm, and incorporation time is 25 minutes.
S3:By the mixed materials of S2 and kaolin according to 96.5:3.5 weight ratio is added in kneading machine together,
It mixes, stir, mediate 30 minutes at room temperature, the water for accounting for material total amount 2% added by this step is added in kneading process so that is all
Mixtures of materials is fully soaked.Kneading machine enables micro mist collection system immediately after opening, and the electric machine frequency of air-introduced machine is transferred to
30Hz。
S4：Material after S3 kneadings is squeezed into strip with banded extruder；
S5：By the strip after S4 extrusions in drying in oven, the drying temperature is 100 DEG C, and the drying time is 2
Hour；
S6：Semi-finished product after S5 is dried roast 2.5 hours under 500 DEG C of air atmospheres, obtain desulfurizing agent 1.
Embodiment 2
The preparation process of desulfurizing agent includes the following steps in the present embodiment：
S1：Zinc oxide purchased in market is sieved by shaking screen, and is the raw material powder of 0.38kg/l by heap density after screening
It collects spare；The raw material powder collected by micro mist collection system (the raw material powder hereinafter referred to as collected) is sieved by shaking screen
Point, and the raw material powder collection that heap density after screening is 0.20kg/l is spare；
S2：The spare raw material powder of the collection of zinc oxide purchased in market and 2 parts by weight after the screening of 95 parts by weight is added to material
It is mixed in bucket mixing machine, mixing rotating speed is 15rpm, and incorporation time is 30 minutes.
S3：By the mixed materials of S2 and clay according to 97:3 weight ratio is added in kneading machine together, at room temperature
Mixing, is mediated 30 minutes at stirring, the water for accounting for material total amount 2.5% added by this step is added in kneading process so that all materials
Mixture is fully soaked.Kneading machine enables micro mist collection system immediately after opening, and the electric machine frequency of air-introduced machine is transferred to 20Hz.
S4：Material after S3 kneadings is squeezed into strip with banded extruder；
S5：By the strip after S4 extrusions in drying in oven, the drying temperature is 100 DEG C, and the drying time is
2.5 hour；
S6：Semi-finished product after S5 is dried roast 2 hours under 550 DEG C of air atmospheres, obtain desulfurizing agent 2.
Embodiment 3
The preparation process of desulfurizing agent includes the following steps in the present embodiment：
S1：Zinc oxide purchased in market is sieved by shaking screen, and is the raw material powder of 0.30kg/l by heap density after screening
It collects spare；The raw material powder collected by micro mist collection system (the raw material powder hereinafter referred to as collected) is sieved by shaking screen
Point, and the raw material powder collection that heap density after screening is 0.12kg/l is spare；
S2：Zinc oxide purchased in market after the screening of the 97 parts by weight raw material powder spare with the collection of 1.5 parts by weight is added to
It is mixed in hopper mixing machine, mixing rotating speed is 15rpm, and incorporation time is 35 minutes.
S3:By the mixed materials of S2 and cement according to 98.5:1.5 weight ratio is added in kneading machine together, in room
Temperature lower mixing, is mediated 35 minutes at stirring, the water for accounting for material total amount 2% added by this step is added in kneading process so that property
Material mixture is fully soaked.Kneading machine enables micro mist collection system immediately after opening, and the electric machine frequency of air-introduced machine is transferred to 15Hz.
S4：Material after S3 kneadings is squeezed into strip with banded extruder；
S5：By the strip after S4 extrusions in drying in oven, the drying temperature is 110 DEG C, and the drying time is 2
Hour；
S6：Semi-finished product after S5 is dried roast 3 hours under 500 DEG C of air atmospheres, obtain desulfurizing agent 3.
Embodiment 4
The preparation process of desulfurizing agent includes the following steps in the present embodiment：
S1：Zinc oxide purchased in market is sieved by shaking screen, and is the raw material powder of 0.35kg/l by heap density after screening
It collects spare；The raw material powder collected by micro mist collection system (the raw material powder hereinafter referred to as collected) is sieved by shaking screen
Point, and the raw material powder collection that heap density after screening is 0.24kg/l is spare；
S2：Zinc oxide purchased in market after the screening of the 92 parts by weight raw material powder spare with the collection of 3.5 parts by weight is added to
It is mixed in hopper mixing machine, mixing rotating speed is 20rpm, and incorporation time is 30 minutes.
S3：By the mixed materials of S20 and dried starch according to 95.5:4.5 weight ratio is added in kneading machine together,
It mixes, stir, mediate 30 minutes at room temperature, the water for accounting for material total amount 3.5% added by this step is added in kneading process so that institute
There is mixtures of materials fully to be soaked.Kneading machine enables micro mist collection system immediately after opening, and the electric machine frequency of air-introduced machine is transferred to
35Hz。
S4：Material after S30 kneadings is squeezed into strip with banded extruder；
S5：By the strip after S40 extrusions in drying in oven, the drying temperature is 100 DEG C, and the drying time is
2.5 hour；
S6：Semi-finished product after S50 is dried roast 2 hours under 550 DEG C of air atmospheres, obtain desulfurizing agent 4.
The related test results of the desulfurizing agent of embodiment 1- embodiments 4 are as shown in table 1 below.Wherein, the D10 grain sizes of powder,
D50 grain sizes and D90 grain sizes are measured and (are surveyed three times, be averaged) by laser particle size analyzer, and the working sulfur capacity of desulfurizing agent is 300
DEG C, air speed 1500h-1Under conditions of, by 100ppmH in synthesis gas, natural gas or other unstripped gas2S is removed to the shape of 0.03ppm
It is calculated under state.The porosity of desulfurizing agent is measured using helium-mercury displacement method, and specific surface area is measured using BET method, resistance to crusing
Intensity is measured using detector for strength of particles.
The related test results of 1 embodiment 1- embodiments of table, 4 raw materials used characteristic, hybrid technique parameter and desulfurizing agent
The content that above-described embodiment illustrates should be understood as that these embodiments are only used for being illustrated more clearly that the present invention, without
For limiting the scope of the invention, after having read the present invention, various equivalent forms of the those skilled in the art to the present invention
Modification each fall within the application range as defined in the appended claims.
Claims (9)
1. a kind of high sulfur capacity zinc oxide fine desulfurizer, which is characterized in that by weight, raw material composition includes activated zinc oxide
2-8 parts of 90-98 parts of powder and adhesive, the activated zinc oxide powder includes activated zinc oxide powders A and active oxidation zinc powder
Last B；
Wherein, activated zinc oxide powders A accounts for the 92-98% of active oxidation zinc powder gross mass, and the heap of activated zinc oxide powders A is close
Degree is 0.25-0.40kg/l, and powder D10 grain sizes are 1.5-3 μm, D50 grain sizes are 6-15 μm, D90 grain sizes are 20-30 μm；
Active oxidation zinc powder B accounts for the 2-8% of active oxidation zinc powder gross mass, and the heap density of active oxidation zinc powder B is
0.10-0.25kg/l, powder D10 grain sizes are 0.5-1.5 μm, D50 grain sizes are 2-5 μm, D90 grain sizes are 7-10 μm.
2. high sulfur capacity zinc oxide fine desulfurizer according to claim 1, which is characterized in that the activated zinc oxide powders A
By being obtained after being sieved zinc oxide purchased in market with shaking screen, zinc oxide content 92-95wt%.
3. high sulfur capacity zinc oxide fine desulfurizer according to claim 1, which is characterized in that the active oxidation zinc powder B
Middle zinc oxide content is 85-90wt%.
4. high sulfur capacity zinc oxide fine desulfurizer according to claim 1, which is characterized in that the adhesive be kaolin,
It is one or more in cement, waterglass, clay, dried starch, natural gum.
5. a kind of preparation method of high sulfur capacity zinc oxide fine desulfurizer according to any one of claims 1-4, which is characterized in that
Include the following steps：
S1, activated zinc oxide powders A and active oxidation zinc powder B are weighed according to the ratio, mixed, obtain activated zinc oxide
Powder；
S2, it will be added in kneading machine together with the mixed active oxidation zinc powders of S1 and adhesive, mix, stir at room temperature
It mixes, mediate 15-60min, suitable water is added in kneading process so that all materials mixture is fully soaked；Wherein, water
Additive amount is the 2-5wt% of material total amount；
S3, extrusion forming is carried out to the kneading material finally obtained in S2, obtains high sulfur capacity zinc oxide fine desulfurizer crude green body；
S4, the high sulfur capacity zinc oxide fine desulfurizer crude green body obtained in S3 is placed in baking oven, under the conditions of 90-120 DEG C, dries 2-
4h obtains high sulfur capacity zinc oxide fine desulfurizer semi-finished product；
S5, the high sulfur capacity zinc oxide fine desulfurizer semi-finished product obtained in S4 are placed under 450-600 DEG C of air atmosphere environment, are roasted
2-5h is burnt, high sulfur capacity zinc oxide fine desulfurizer finished product is obtained.
6. preparation method according to claim 5, which is characterized in that in S1, mixing rate 3-20r/min, when mixing
Between be 15-60min.
7. preparation method according to claim 5, which is characterized in that while S2 is proceeded by, system is collected by micro mist
System collects raw material powder.
8. preparation method according to claim 7, which is characterized in that when collecting raw material powder, pass through regulating air volume
Control the heap density and grain size of the powder collected.
9. preparation method according to claim 7, which is characterized in that carried out to the raw material powder of collection by shaking screen
Screening, acquisition heap density is 0.10-0.25 kg/l, powder D10 grain sizes are 0.5-1.5 μm, D50 grain sizes are 2-5 μm, D90 grain sizes
For 7-10 μm of raw material powder, come into operation as active oxidation zinc powder B.
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| CN101970106A (en) * | 2008-03-12 | 2011-02-09 | 约翰森·马瑟公开有限公司 | Desulphurisation material |
| CN104136116A (en) * | 2011-07-27 | 2014-11-05 | 沙特阿拉伯石油公司 | Catalytic compositions useful in removal of sulfur compounds from gaseous hydrocarbons, processes for making these and uses thereof |
| CN105664706A (en) * | 2016-01-19 | 2016-06-15 | 北京三聚环保新材料股份有限公司 | High-sulfur-capacity low-cost desulfurizing agent and preparation method thereof |
| CN105692685A (en) * | 2016-03-17 | 2016-06-22 | 安徽颖达锌业发展有限公司 | Zinc oxide desulphurizer and preparing method thereof |
| CN106512677A (en) * | 2016-10-26 | 2017-03-22 | 北京三聚环保新材料股份有限公司 | Zinc oxide desulfurizer and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101970106A (en) * | 2008-03-12 | 2011-02-09 | 约翰森·马瑟公开有限公司 | Desulphurisation material |
| CN104136116A (en) * | 2011-07-27 | 2014-11-05 | 沙特阿拉伯石油公司 | Catalytic compositions useful in removal of sulfur compounds from gaseous hydrocarbons, processes for making these and uses thereof |
| CN105664706A (en) * | 2016-01-19 | 2016-06-15 | 北京三聚环保新材料股份有限公司 | High-sulfur-capacity low-cost desulfurizing agent and preparation method thereof |
| CN105692685A (en) * | 2016-03-17 | 2016-06-22 | 安徽颖达锌业发展有限公司 | Zinc oxide desulphurizer and preparing method thereof |
| CN106512677A (en) * | 2016-10-26 | 2017-03-22 | 北京三聚环保新材料股份有限公司 | Zinc oxide desulfurizer and preparation method thereof |
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