CN101590359A - Room temperature marsh gas desulfurizer and preparation method thereof - Google Patents
Room temperature marsh gas desulfurizer and preparation method thereof Download PDFInfo
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- CN101590359A CN101590359A CN 200810113033 CN200810113033A CN101590359A CN 101590359 A CN101590359 A CN 101590359A CN 200810113033 CN200810113033 CN 200810113033 CN 200810113033 A CN200810113033 A CN 200810113033A CN 101590359 A CN101590359 A CN 101590359A
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Abstract
The present invention relates to a kind of room temperature marsh gas desulfurizer and preparation method thereof, described biogas desulfurizer comprises carrier, a hydrated ferric oxide, mineral powder and white lime, its preparation method is described mineral powder to be ground the back mix evenly with a hydrated ferric oxide, white lime, through add water mix pinch, extruded moulding and drying, just obtain room temperature marsh gas desulfurizer of the present invention.Biogas desulfurizer of the present invention has overcome that present biogas desulfurizer Sulfur capacity is low, abrasion more greatly, easily harden, shortcoming that service life is short, have the Sulfur capacity height, active good, do not harden, easily preparation, easy advantage such as regeneration.
Description
Technical field
The present invention relates to a kind of room temperature marsh gas desulfurizer and preparation method thereof, belong to gas purification and desulfurizing agent preparation field.
Background technology
Biogas is to utilize various excrements of animals and chemical industry rejectable waste etc. to make a kind of imflammable gas that raw material is produced through anaerobic fermentation.Generally contain methane (CH in the biogas
4) 60%-70%, carbon dioxide (CO
2) 25%-40% and a spot of ammonia (NH
3), hydrogen (H
2) and carbon monoxide (CO), contain a large amount of hydrogen sulfide (H simultaneously
2S).Its hydrogen sulfide content of the biogas that different material is produced has nothing in common with each other, and general hydrogen sulfide content is 1.5-3.5g/m
3
Hydrogen sulfide is a kind of pernicious gas of severe toxicity.Hydrogen sulfide is in air and under the wet environment condition, and to pipeline, burner and other combustion apparatus, measuring instrument etc. have strong corrosiveness; Sulfur dioxide (the SO that generates behind the sulfureted hydrogen burning
2) meet water generation sulfuric acid molecule, hardware, contaminated environment around can corroding again, and directly endanger the healthy of people.The environmental protection standard in China strict regulations, hydrogen sulfide content must not surpass 20mg/m in the biogas
3, so biogas to carry out desulfurization before use be essential.
People develop a lot of biogas desulfurization technology and biogas desulfurizer for this reason, common biogas desulfurizer has active carbon, zinc oxide, manganese oxide, molecular sieve or iron oxide etc., above-mentioned biogas desulfurizer is considered from composite factors such as the duration of runs, serviceability temperature, prices, using maximum biogas desulfurizers at present is ferric oxide desulfurizer, but the defective that the ferric oxide desulfurizer existence is easily hardened, the accumulative total Sulfur capacity is low and service life is short.
A kind of amorphous desulfurizing agent is disclosed in publication number is the Chinese patent literature of CN1616139A, this desulfurizing agent can be widely used in the technology of box or tower gas at normal temperature dry removal hydrogen sulfide at present, it is to be rich in iron, manganese, copper, the manganese ore powder of multiple metal symbiosis such as zinc is a main component, also comprise lignin, desulfurizing assistant agent and water, the initial Sulfur capacity of this desulfurizing agent is greater than 7%, three accumulative total Sulfur capacity are greater than 23%, improved the defective that the initial Sulfur capacity of the amorphous desulfurizing agent of current ambient temperature hangs down and easily hardens, yet it exists still service life not long, initial Sulfur capacity and the high inadequately shortcoming of accumulative total Sulfur capacity.
A kind of solid regenerative gas desulfurizing agent and regeneration technology thereof are disclosed in notification number is the Chinese patent literature of CN1075832C, described gas desulfurizer is made up of the ferrous sulfate of 40-50%, the calcium hydroxide of 40-50%, the copper sulphate of 0.4-0.8% and the plaster of paris of 5-10%, its advantage is that desulfurized effect is good, long service life, no spontaneous combustion, avirulence, yet it exists initial Sulfur capacity and the not high shortcoming of accumulative total Sulfur capacity.
Summary of the invention
For this reason, technical problem to be solved by this invention be to propose a kind of Sulfur capacity height, active good, do not harden, the room temperature marsh gas desulfurizer of easily preparation, easily regeneration and preparation method thereof.
Another technical problem to be solved by this invention is to propose room temperature marsh gas desulfurizer that a kind of preparation technology is simple and production cost is low and preparation method thereof.
For solving the problems of the technologies described above, a kind of room temperature marsh gas desulfurizer of the present invention, it is made up of carrier, a hydrated ferric oxide, white lime, bastnasite breeze and/or ore deposit pyrolusite powder.
Described carrier is a porous carrier.Described porous carrier is any one in aluminium oxide, coal mass active carbon or the wood activated charcoal.
The weight percentage of each component in the described room temperature marsh gas desulfurizer: carrier is 20-60%, and a hydrated ferric oxide is 10-30%, and white lime is 5-20%, and pyrolusite is 0-20%, and bastnasite is 0-10%.
The method for preparing described room temperature marsh gas desulfurizer, comprise with after bastnasite breeze and/or the grinding of ore deposit pyrolusite, mix that water is mixed to be pinched through adding then with a hydrated ferric oxide, white lime and carrier, extruded moulding and drying steps promptly obtain described room temperature marsh gas desulfurizer.
Particle order number after described bastnasite and/or pyrolusite grind is more than or equal to 160 orders.Described baking temperature is 30～100 ℃.
Technique scheme of the present invention compared with prior art has the following advantages, (1) biogas desulfurizer of the present invention is made up of porous carrier, a hydrated ferric oxide, white lime, bastnasite breeze and/or pyrolusite powder, wherein white lime is binding agent, one hydrated ferric oxide is a main active component, because a hydrated ferric oxide has preferably the ability with the sulfide combination, therefore desulfurized effect is good, the Sulfur capacity height; The use of porous carrier among the present invention has improved the Sulfur capacity of desulfurizing agent, has reduced abrasion, makes desulfurizing agent be difficult for hardening.The existence of rare-earth mineral powder and pyrolusite has then effectively improved the desulphurizing ability of desulfurizing agent, has improved desulfurization performance, simultaneously owing to the oxygen ability of storing of rare earth oxide, has improved the regenerability of desulfurizing agent effectively.So biogas desulfurizer of the present invention has initial Sulfur capacity and accumulative total Sulfur capacity height, active good, do not harden, easily regeneration has the advantage of higher mechanical properties and water resistance; (2) employing is of the present invention with porous carrier, a hydrated ferric oxide, white lime and bastnasite and/or the mixed method for preparing biogas desulfurizer of pyrolusite, technology is simple, raw material sources are extensive, do not need to carry out high-temperature roasting, have the low advantage of production cost.
The specific embodiment
MnO in the used pyrolusite of following examples
2Content be 50%～70%, the content of cerium oxide is 70%～80% in the bastnasite.The preparation method of a used hydrated ferric oxide is in following examples, with FeSO
47H
2The water-soluble wiring solution-forming of O carries out titration with NaOH solution to it, works as FeSO
47H
2The complete post precipitation of ferrous ion in the O solution filters, washes, and dries naturally in air, promptly obtains a hydrated ferric oxide.
Embodiment 1
1.5kg one hydrated ferric oxide, 0.5kg white lime and 2kg coal mass active carbon are mixed, add water mix pinch, extruded moulding, 30 ℃ of dryings just obtain biogas desulfurizer product A-1 of the present invention.
Embodiment 2
1.0kg pyrolusite and 0.5kg bastnasite are pulverized, ground, sieve through 160 orders, obtain mixture, then powder and 1.0kg one hydrated ferric oxide, 0.75kg white lime and 1.75kg coal mass active carbon are mixed, add water mix pinch, extruded moulding, 35 ℃ of dryings just obtain biogas desulfurizer product A-2 of the present invention.
Embodiment 3
1.0kg pyrolusite and 0.25kg bastnasite are pulverized, ground, sieve through 160 orders, obtain mixture, then powder and 0.5kg one hydrated ferric oxide, 1.0kg white lime and 2.25kg coal mass active carbon are mixed, add water mix pinch, extruded moulding, 35 ℃ of dryings just obtain biogas desulfurizer product A-3 of the present invention.
Embodiment 4
0.5kg pyrolusite and 0.25kg bastnasite are pulverized, ground, sieve through 160 orders, obtain mixture, then powder and 1.0kg one hydrated ferric oxide, 0.5kg white lime and 3.0kg coal mass active carbon are mixed, add water mix pinch, extruded moulding, 35 ℃ of dryings just obtain biogas desulfurizer product A-4 of the present invention.
Embodiment 5
1.5kg one hydrated ferric oxide, 0.5kg white lime and 2kg wood activated charcoal are mixed, add water mix pinch, extruded moulding, 30 ℃ of dryings just obtain biogas desulfurizer product B-1 of the present invention.
Embodiment 6
1.0kg pyrolusite and 0.5kg bastnasite are pulverized, ground, sieve through 160 orders, obtain mixture, then powder and 1.0kg one hydrated ferric oxide, 0.75kg white lime and 1.75kg wood activated charcoal are mixed, add water mix pinch, extruded moulding, 35 ℃ of dryings just obtain biogas desulfurizer product B-2 of the present invention.
Embodiment 7
1.0kg pyrolusite and 0.25kg bastnasite are pulverized, ground, sieve through 160 orders, obtain mixture, then powder and 0.5kg one hydrated ferric oxide, 1.0kg white lime and 2.25kg wood activated charcoal are mixed, add water mix pinch, extruded moulding, 35 ℃ of dryings just obtain biogas desulfurizer product B-3 of the present invention.
Embodiment 8
0.5kg pyrolusite and 0.25kg bastnasite are pulverized, ground, sieve through 160 orders, obtain mixture, then powder and 1.0kg one hydrated ferric oxide, 0.5kg white lime and 3.0kg wood activated charcoal are mixed, add water mix pinch, extruded moulding, 30 ℃ of dryings just obtain biogas desulfurizer product B-4 of the present invention.
Embodiment 9
1.5kg one hydrated ferric oxide, 0.5kg white lime and 2kg aluminium oxide are mixed, add water mix pinch, extruded moulding, 30 ℃ of dryings just obtain biogas desulfurizer products C-1 of the present invention.
Embodiment 10
1.0kg pyrolusite and 0.5kg bastnasite are pulverized, ground, sieve through 160 orders, obtain mixture, then powder and 1.0kg one hydrated ferric oxide, 0.75kg white lime and 1.75kg aluminium oxide are mixed, add water mix pinch, extruded moulding, 35 ℃ of dryings just obtain biogas desulfurizer products C-2 of the present invention.
Embodiment 11
1.0kg pyrolusite and 0.25kg bastnasite are pulverized, ground, sieve through 160 orders, obtain mixture, then powder and 0.5kg one hydrated ferric oxide, 1.0kg white lime and 2.25kg aluminium oxide are mixed, add water mix pinch, extruded moulding, 35 ℃ of dryings just obtain biogas desulfurizer products C-3 of the present invention.
Embodiment 12
0.5kg pyrolusite and 0.25kg bastnasite are pulverized, ground, sieve through 160 orders, obtain mixture, then powder and 1.0kg one hydrated ferric oxide, 0.5kg white lime and 3.0kg aluminium oxide are mixed, add water mix pinch, extruded moulding, 30 ℃ of dryings just obtain biogas desulfurizer products C-4 of the present invention.
Estimate Sulfur capacity under oxygen free condition, step is as follows: with product 90 ℃ dry 1 hour down, grind with mortar then, cross the 80-160 mesh sieve.Accurately take by weighing the product (claiming accurate to 0.0001g) after 1g sieves, described product is filled in the glass reaction tube, loading height is about about 3-4cm, and cotton is filled at two ends.Reaction tube one termination H
2S standard gas (H
2S concentration is 4%), a termination has 0.1mol/L AgNO
3Reactor on.Open H
2S gas cylinder valve, the about 200-400/h of control air speed.When AgNO is housed
3Reactor in when just black precipitate having occurred, valve-off stops experiment.After recording Sulfur capacity, the described glass reaction tube that is filled with desulfurizing agent dried 48 hours naturally in air after, continue above experiment and survey its secondary Sulfur capacity.The determination step of three times, four times and No. five times Sulfur capacity is the same.
Following table 1 is the desulphurizing activated evaluation of the resulting product of the embodiment of the invention.
Table 1
| Product | Air speed h -1 | A Sulfur capacity % | Secondary Sulfur capacity % | No. three Sulfur capacity % | No. four Sulfur capacity % | No. five Sulfur capacity % | Five accumulative total Sulfur capacity % | Mechanical strength N/cm |
| A-1 | 400 | 30 | 28 | 21 | 10 | 5 | 94 | 89 |
| A-2 | 400 | 27 | 25 | 19 | 8 | 4 | 83 | 90 |
| A-3 | 400 | 25 | 21 | 18 | 9 | 5 | 78 | 91 |
| A-4 | 400 | 33 | 31 | 24 | 13 | 7 | 108 | 87 |
| B-1 | 400 | 29 | 28 | 16 | 7 | 3 | 83 | 90 |
| B-2 | 400 | 27 | 25 | 14 | 6 | 3 | 75 | 91 |
| B-3 | 400 | 24 | 21 | 15 | 8 | 4 | 72 | 89 |
| B-4 | 400 | 30 | 27 | 14 | 6 | 5 | 82 | 87 |
| C-1 | 400 | 30 | 27 | 17 | 9 | 2 | 85 | 97 |
| C-2 | 400 | 27 | 24 | 15 | 9 | 3 | 78 | 95 |
| C-3 | 400 | 26 | 23 | 12 | 5 | 2 | 68 | 91 |
| C-4 | 400 | 33 | 29 | 18 | 10 | 3 | 93 | 89 |
By table 1 as seen, Sulfur capacity of biogas desulfurizer of the present invention and accumulative total Sulfur capacity height, mechanical strength is good, and therefore biogas desulfurizer of the present invention has the high and active good advantage of Sulfur capacity.
Obviously, the foregoing description only is for example clearly is described, and is not the qualification to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And conspicuous variation of being extended out thus or change still are among the protection domain of claim of the present invention.
Claims (8)
1. room temperature marsh gas desulfurizer, it is characterized in that: described room temperature marsh gas desulfurizer is made up of carrier, a hydrated ferric oxide, white lime, bastnasite breeze and/or ore deposit pyrolusite powder.
2. room temperature marsh gas desulfurizer according to claim 1 is characterized in that: described carrier is a porous carrier.
3. room temperature marsh gas desulfurizer according to claim 2 is characterized in that: described porous carrier is any one in aluminium oxide, coal mass active carbon or the wood activated charcoal.
4. according to any described room temperature marsh gas desulfurizer among the claim 1-3, it is characterized in that: the weight percentage of each component is in the described desulfurizing agent:
Carrier 20-60%
One hydrated ferric oxide 10-30%
White lime 5-20%
Pyrolusite 0-20%
Bastnasite 0-10%.
5. the method for preparing any described room temperature marsh gas desulfurizer among the claim 1-4, it is characterized in that: described method comprises after bastnasite and/or the pyrolusite grinding, mix with a hydrated ferric oxide, white lime and carrier, water is mixed to be pinched through adding then, extruded moulding and drying steps promptly obtain described room temperature marsh gas desulfurizer.
6. room temperature marsh gas desulfurizer according to claim 5 is characterized in that: the particle order number after described bastnasite and/or pyrolusite grind is more than or equal to 160 orders.
7. room temperature marsh gas desulfurizer according to claim 6 is characterized in that: described carrier is any one in aluminium oxide, coal mass active carbon or the wood activated charcoal.
8. room temperature marsh gas desulfurizer according to claim 7 is characterized in that: described baking temperature is 30～100 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897786A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Synthesis method for hierarchically porous ZIF-8 and preparation method for deep desulfurizing agent |
| CN106621779A (en) * | 2017-01-09 | 2017-05-10 | 昆明理工大学 | Preparation method of manganese slag slurry capable of simultaneously removing H2S (hydrogen sulfide), PH3 (hydrogen phosphide) and HCN (hydrogen cyanide) |
| CN106944077A (en) * | 2017-04-06 | 2017-07-14 | 湖南三友环保科技股份有限公司 | Preparation method for the sulfur removal material of marsh gas purifying |
| CN108722168A (en) * | 2018-06-15 | 2018-11-02 | 西南化工研究设计院有限公司 | A kind of renewable dry flue gas desulphurization agent and its preparation method and application |
| CN109482144A (en) * | 2018-12-29 | 2019-03-19 | 山东华泰纸业股份有限公司 | A kind of desulfurization removes the preparation method of carbon adsorbent |
| CN111330424A (en) * | 2020-01-20 | 2020-06-26 | 北京宝聚能源科技有限公司 | Flue gas desulfurizing agent and preparation method and application thereof |
-
2008
- 2008-05-27 CN CN 200810113033 patent/CN101590359A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897786A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Synthesis method for hierarchically porous ZIF-8 and preparation method for deep desulfurizing agent |
| CN102897786B (en) * | 2012-10-16 | 2014-10-15 | 中国石油大学(北京) | Synthesis method for hierarchically porous ZIF-8 and preparation method for deep desulfurizing agent |
| CN106621779A (en) * | 2017-01-09 | 2017-05-10 | 昆明理工大学 | Preparation method of manganese slag slurry capable of simultaneously removing H2S (hydrogen sulfide), PH3 (hydrogen phosphide) and HCN (hydrogen cyanide) |
| CN106621779B (en) * | 2017-01-09 | 2019-09-27 | 昆明理工大学 | It is a kind of for simultaneously remove hydrogen sulfide, hydrogen phosphide and hydrogen cyanide manganese ore dreg slurry preparation method |
| CN106944077A (en) * | 2017-04-06 | 2017-07-14 | 湖南三友环保科技股份有限公司 | Preparation method for the sulfur removal material of marsh gas purifying |
| CN106944077B (en) * | 2017-04-06 | 2019-12-27 | 湖南三友环保科技有限公司 | Preparation method of desulfurization material for biogas purification |
| CN108722168A (en) * | 2018-06-15 | 2018-11-02 | 西南化工研究设计院有限公司 | A kind of renewable dry flue gas desulphurization agent and its preparation method and application |
| CN109482144A (en) * | 2018-12-29 | 2019-03-19 | 山东华泰纸业股份有限公司 | A kind of desulfurization removes the preparation method of carbon adsorbent |
| CN111330424A (en) * | 2020-01-20 | 2020-06-26 | 北京宝聚能源科技有限公司 | Flue gas desulfurizing agent and preparation method and application thereof |
| CN111330424B (en) * | 2020-01-20 | 2020-11-27 | 北京宝聚能源科技有限公司 | Flue gas desulfurizing agent and preparation method and application thereof |
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Application publication date: 20091202 |