CN105582877A - Normal-temperature desulfurization dearsenic agent and preparation method thereof - Google Patents
Normal-temperature desulfurization dearsenic agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a normal-temperature desulfurization dearsenic agent and a preparation method thereof. The invention mainly aims at solving problems of high bulk density, low sulfur capacity and low arsenic capacity of desulfurization dearsenic agents in prior arts. The desulfurization dearsenic agent provided by the invention comprises the following components, by weight: (a) 1-10 parts of aurichalcite, (10) 10-50 parts of copper oxide, (c) 10-60 parts of zinc oxide, and (d) 0.01-3 parts of rare earth metal R. With the above technical scheme, the problem is well solved. The method can be applied in the purification of natural gas, synthetic gas, light gas-liquid hydrocarbons, and the like.
Description
Technical field
The present invention relates to a kind of normal temperature desulfurating and dearsenic agent and preparation method thereof.
Background technology
The impurity such as sulphur arsenic are extensively present in the raw materials such as natural gas, synthesis gas, coal gas, lightweight liquid state hydro carbons, and these are assortedThe existence of matter can cause a lot of catalyst poisoning inactivations, greatly shortens catalyst life, even causes the catalytic reaction cannot be normalCarry out; In addition, do not remove clean sulphur arsenic impurities can along with produce enter in the composite of downstream, thereby bring one to beThe problem of the aspects such as the Environmental Health of row. Therefore, remove the master of the impurity such as sulphur arsenic for protection downstream unit high-efficiency high-accuracyCatalyst and the quality that simultaneously improves downstream product have very important meaning.
Generally, the sulphur-containing substance existing in the raw material of industry is mainly H2S and COS, for these sulphur-containing substancesWhat deep removal effect was best is Zinc oxide desulfurizer. Zinc oxide desulfurization with its desulfurization precision high, easy to use, safe reliable,Sulfur capacity is high, play " checking on " and " protection " effect and occupy very important status, it be applied in widely synthetic ammonia,The industries such as hydrogen manufacturing, Coal Chemical Industry, petroleum refinement, beverage production, with remove natural gas, petroleum distillate, casing-head gas, refinery gas,Hydrogen sulfide in the raw material such as synthesis gas, carbon dioxide and some organic sulfur. Zinc sulphide desulfurization can be removed to the sulphur in unstripped gas0.055mg/kg. In normal temp zinc oxide desulfuriging agent, add CuO to improve its desulphurizing ability. Zinc oxide desulfurizer is generally used for essenceSweetening process, it also can absorb general organosulfur compound. Arsenic impurities in the raw material of industry, conventionally with AsH3Form is deposited, it is four classes that the Hydrodearsenic Catalyst of industrial use roughly can be divided into copper system, plumbous system, manganese system and nickel, wherein comparatively common with copper system.Copper based de-arsenic catalyst arsenic holds high, can under normal temperature, normal pressure and higher space velocity, carry out. Copper based de-arsenic catalyst can be divided into again metallic copper,CuO-Al2O3、CuO-ZnO-Al2O3Deng. When taking CuO as active component, AsH3By Cu2+Be reduced to low price or metalState, arsenic is combined with copper or is dissociated into element state. The development trend of desulfurizing agent and Hydrodearsenic Catalyst be to low bulk density, low serviceability temperature,The future development that high strength and high Sulfur capacity and arsenic hold.
Patent CN101591554A discloses a kind of normal temperature composite desulfurating and dearsenic agent and preparation method thereof, this desulfurating and dearsenic agentBe made up of carrier and active component, active component is lead oxide, magnetic oxide and cupric oxide, and carrier is γ-Al2O3, this is de-Sulphur Hydrodearsenic Catalyst need to, 350～650 DEG C of activation 4～8 hours, can be found out this oxide desulfurization from its composition and preparation methodHydrodearsenic Catalyst bulk density is high, preparation process complexity, and commercial Application cost is higher.
Patent CN102049236A discloses a kind of copper zinc ambient temperature desulfuration agent and preparation method thereof, and this desulfurizing agent is by alkali formulaZinc carbonate, basic copper carbonate and binding agent composition, the preparation of this desulfurization sulfur agent is by commercially available basic zinc carbonate, basic carbonateCopper, binding agent and water are mediated, moulding, obtain after dry, and this desulfurizing agent obtains by physical mixed, thereby whereinZinc-copper active component cannot be brought into play synergy, thereby causes its Sulfur capacity lower.
Summary of the invention
Technical problem to be solved by this invention is that in prior art, desulfurating and dearsenic agent bulk density is high, and Sulfur capacity and arsenic hold low askingTopic, provides a kind of new desulfurating and dearsenic agent and preparation method thereof. This desulfurating and dearsenic agent contains aurichalcite and CuO-ZnO classSolid solution, has bulk density low, and Sulfur capacity and arsenic hold high advantage.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: by a kind of desulfurating and dearsenic agent, with weight portionNumber meter, comprises following component: a) aurichalcite of 1～10 part; B) cupric oxide of 10～50 parts; C) zinc oxide of 10～60 parts;D) the rare earth metal R of 0.01～3 part.
In technique scheme, in desulfurating and dearsenic agent parts by weight, the preferable range of described aurichalcite is 2～8 parts; InstituteThe preferable range of stating cupric oxide is 13～48; The preferable range of described zinc oxide zinc is 15～55 parts; Described rare earth metal R containsAmount is 0.02～2 part; Described rare earth metal R is at least one in lanthanum, cerium, yttrium; Desulfurating and dearsenic agent bulk density is less than1.0kg/m3, side pressure strength is greater than 70N/ grain.
The preparation method of described normal temperature desulfurating and dearsenic agent, in turn includes the following steps:
(1) by the nitrate of copper nitrate, zinc nitrate, aluminum nitrate, R and hydromassage that ratio meter: Cu/Zn is 0.1～2; Al/ZnBe 0～0.8; R/ (Cu+Zn+Al) is 0.002～1; (Cu+Zn+Al+M)/H2O is 0.01～0.04 ratio mixing, stirs allThe even solution I that obtains;
(2) by least one and hydromassage in sodium carbonate, sodium acid carbonate, ammonium carbonate you than the ratio mixing that is 0.01～0.04,Solution II stirs to obtain;
(3) solution I and II are mixed, at 40～90 DEG C, react 0.5～3 hour to obtain sediment, by dry sediment washingDry;
(4) sediment, binding agent, mix lubricant are rolled evenly, add the water of 10～50 % by weight, granulation;
(5) by powder good granulation at 170～300 DEG C, roasting 1～5 hour;
(6) compression molding is desulfurating and dearsenic agent.
In technique scheme, the water yield adding in step (4) is that gross weight taking sediment, binding agent and lubricant is as benchmark.
Normal temperature desulfurating and dearsenic agent of the present invention, owing to containing aurichalcite, its volume is larger, in banking process, can produceLarger duct, thereby its bulk density is lower. The CuO-ZnO class solid solution forming after aurichalcite heat treatment, such is solidThe CuO more ZnO that around arranges in solution, in like manner, the ZnO more CuO that around also arranged, can ensure CuO andThe abundant refinement of ZnO, makes CuO particle greatly increase with the chance that ZnO granular boundary contacts, and provides in more activityThe heart. Adding of rare earth metal, improve Zn, Cu CHARGE DISTRIBUTION around, be conducive to the raising of its detergent power. ThisBrightly obtain good technique effect.
Normal temperature desulfurating and dearsenic agent of the present invention can be used in the purification of natural gas, synthesis gas, lightweight liquid state hydro carbons etc. ?Normal temperature, normal pressure, volume space velocity are 3000h-1Condition under, with the nitrogen containing variable concentrations sulphur, arsenic compound impurity or syntheticGas is by reactor, and the Sulfur capacity of adsorbent can reach more than 20%. Be that 3.0MPa, mass space velocity are 3.5h at normal temperature, pressure-1Condition under, with the propylene liguid containing variable concentrations sulphur, arsenic compound impurity, by reactor, the Sulfur capacity of adsorbent also can reachMore than 20%.
Below by embodiment, the invention will be further elaborated.
Brief description of the drawings
Fig. 1 is the XRD diffraction spectrogram of preparing adsorbent. (characteristic diffraction peak of aurichalcite is in 2 θ=13.0 °; Cupric oxideDiffraction maximum in 2 θ=35.49 ° with 38.73 °; The characteristic diffraction peak of zinc oxide is in 2 θ=31.8 °, 36.2 ° and 56.6 °)
Detailed description of the invention
[comparative example 1]
Comparative example 1 synthetic sample is zinc oxide.
By 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates and 500 kilograms of mixing and stirring of water obtain metal salt solution, by carbon550 kilograms, 30 kilograms, sodium of acid and water mix and obtain sodium carbonate liquor, and sodium carbonate liquor is mixed all with metal salt solutionEven, 70 DEG C of reactions 1 hour, by dry sediment washing, add 6 kg of alumina, 1 kilogram of graphite mixing rolls,Then add the water of 30 % by weight, granulation, 300 DEG C of roastings 3 hours, compression molding, obtains sample sets prejudice table 1.
[comparative example 2]
Comparative example 2 synthetic samples are cupric oxide.
By 30 kilograms of copper nitrates, 10 kilograms of aluminum nitrates and 500 kilograms of mixing and stirring of water obtain metal salt solution, by carbon550 kilograms, 30 kilograms, sodium of acid and water mix and obtain sodium carbonate liquor, and sodium carbonate liquor is mixed all with metal salt solutionEven, 70 DEG C of reactions 1 hour, by dry sediment washing, add 6 kg of alumina, 1 kilogram of graphite mixing rolls,Then add the water of 30 % by weight, granulation, 300 DEG C of roastings 3 hours, compression molding, obtains sample sets prejudice table 1.
[comparative example 3]
Comparative example 3 synthetic samples are the cupric oxide zinc oxide that does not contain aurichalcite.
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates and 500 kilograms of mixing and stirring of water obtainMetal salt solution, mixes 550 kilograms, 30 kilograms, sodium carbonate and water to obtain sodium carbonate liquor, by sodium carbonate liquor withMetal salt solution mixes, and 70 DEG C of reactions 1 hour, by dry sediment washing, adds 6 kg of alumina, 1,000Gram graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, and 350 DEG C of roastings 5 hours, compression molding, obtains sampleProduct form in table 1.
[comparative example 4]
Comparative example 4 synthetic samples are the desulfurating and dearsenic agent that does not contain rare earth metal.
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates and 500 kilograms of mixing and stirring of water obtainMetal salt solution, mixes 550 kilograms, 30 kilograms, sodium carbonate and water to obtain sodium carbonate liquor, by sodium carbonate liquor withMetal salt solution mixes, and 70 DEG C of reactions 1 hour, by dry sediment washing, then adds 6 kg of alumina,1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, and 270 DEG C of roastings 2 hours, compression molding,To sample sets prejudice table 1.
[embodiment 1]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 1.0 kilograms of cerous nitrates and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 270 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 2]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 0.02 kilogram of cerous nitrate and waterMixing and stirring obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 270 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 3]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 0.1 kilogram of cerous nitrate and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 270 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 4]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 0.5 kilogram of cerous nitrate and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 270 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 5]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 1.5 kilograms of cerous nitrates and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 270 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 6]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 2.0 kilograms of cerous nitrates and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 270 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 7]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 1.0 kilograms of lanthanum nitrates and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 270 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 8]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 0.9 kilogram of yttrium nitrate and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 270 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 9]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 1.0 kilograms of cerous nitrates and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 280 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 10]
By 30 kilograms of copper nitrates, 40 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 1.0 kilograms of cerous nitrates and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 290 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
[embodiment 11]
By 6 kilograms of copper nitrates, 8 kilograms of zinc nitrates, 2 kilograms of aluminum nitrates, 1.0 kilograms of cerous nitrates and water double centner mixStir and obtain metal salt solution, 6 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 110 kilograms, water, by carbonAcid sodium solution mixes with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then adds 1,000Gram aluminium oxide, 0.2 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 300 DEG C of roastings 2 hours, pressSheet moulding, obtains sample sets prejudice table 1.
[embodiment 12]
By 60 kilograms of copper nitrates, 10 kilograms of zinc nitrates, 10 kilograms of aluminum nitrates, 500 kilograms, 1.0 kilograms of cerous nitrates and water are mixedClosing stirs obtains metal salt solution, and 30 kilograms, sodium carbonate is mixed and obtains sodium carbonate liquor with 550 kilograms, water,Sodium carbonate liquor is mixed with metal salt solution, 70 DEG C of reactions 1 hour, by dry sediment washing, then add6 kg of alumina, 1 kilogram of graphite mixes and rolls, and then adds the water of 30 % by weight, granulation, 270 DEG C of roastings 2 hours,Compression molding, obtains sample sets prejudice table 1.
Table 1
[embodiment 13]
Desulfurating and dearsenic agent prepared by above-described embodiment is ground into 20～40 object particles, and filling it into internal diameter is the anti-of 1cmAnswering in device, is 3000h at normal temperature, normal pressure, volume space velocity-1Condition under, with containing variable concentrations sulphur, arsenic compound impurityNitrogen, by this reactor, is evaluated this desulfurating and dearsenic agent, and result is as shown in table 2.
Table 2
[embodiment 14]
Desulfurating and dearsenic agent prepared by above-described embodiment is ground into 20～40 object particles, and filling it into internal diameter is the anti-of 1cmAnswering in device, is 3000h at normal temperature, normal pressure, volume space velocity-1Condition under, with containing variable concentrations sulphur, arsenic compound impuritySynthesis gas, by this reactor, is evaluated this desulfurating and dearsenic agent, and result is as shown in table 3.
Table 3
[embodiment 15]
Desulfurating and dearsenic agent prepared by above-described embodiment is ground into 20～40 object particles, and filling it into internal diameter is the anti-of 1cmAnswering in device, is 3.5h at normal temperature, pressure 3.0MPa, mass space velocity-1Condition under, with containing variable concentrations sulphur, arsenic compoundThe propylene liguid of impurity, by this reactor, is evaluated this desulfurating and dearsenic agent, and result is as shown in table 4.
Table 4
Claims (9)
1. a desulfurating and dearsenic agent, in parts by weight, comprises following component:
A) aurichalcite of 1～10 part;
B) cupric oxide of 10～50 parts;
C) zinc oxide of 10～60 parts;
D) the rare earth metal R of 0.01～3 part.
2. desulfurating and dearsenic agent according to claim 1, is characterized in that in desulfurating and dearsenic agent parts by weight green copper zincMineral content is 2～8 parts.
3. desulfurating and dearsenic agent according to claim 1, is characterized in that in desulfurating and dearsenic agent parts by weight, cupric oxideContent is 13～48 parts.
4. desulfurating and dearsenic agent according to claim 1, is characterized in that in desulfurating and dearsenic agent parts by weight, zinc oxideContent is 15～55 parts.
5. desulfurating and dearsenic agent according to claim 1, is characterized in that in desulfurating and dearsenic agent parts by weight rare earth goldBelonging to R content is 0.02～2 part.
6. desulfurating and dearsenic agent according to claim 1, it is characterized in that rare earth metal R be in lanthanum, cerium, yttrium at leastA kind of.
7. desulfurating and dearsenic agent according to claim 1, is characterized in that the bulk density of desulfurating and dearsenic agent is less than 1.0kg/m3，Side pressure strength is greater than 70N/ grain.
8. the preparation method of the desulfurating and dearsenic agent described in claim 1～7 any one, comprises the following steps successively:
(1) by the nitrate of copper nitrate, zinc nitrate, aluminum nitrate, R and hydromassage that ratio meter: Cu/Zn is 0.1～2;Al/Zn is 0～0.8; R/ (Cu+Zn+Al) is 0.002～1; (Cu+Zn+Al+M)/H2O is that 0.01～0.04 ratio is mixedClose, solution I stirs to obtain;
(2) by least one and hydromassage in sodium carbonate, sodium acid carbonate, ammonium carbonate you than the ratio that is 0.01～0.04Mix, solution II stirs to obtain;
(3) solution I and II are mixed, at 40～90 DEG C, react 0.5～3 hour to obtain sediment, sediment is washedWash dry;
(4) sediment, binding agent, mix lubricant are rolled evenly, add the water of 10～50 % by weight, granulation;
(5) by powder good granulation at 170～300 DEG C, roasting 1～5 hour;
(6) compression molding is desulfurating and dearsenic agent.
9. the desulfurating and dearsenic agent described in claim 1～7 any one is used for to natural gas, synthesis gas, lightweight liquid state hydro carbonsPurification in.
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| CN107952412A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Sulphur, arsenic, phosphorus cleanser and preparation method thereof |
| CN107952409A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Sulphur, arsenic, phosphorus adsorbent and preparation method thereof |
| CN107952408A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Sulphur, arsenic, phosphorus cleanser and preparation method thereof |
| CN107952411A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Sulphur, arsenic, phosphorus cleanser and preparation method thereof |
| CN107952410A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Sulphur, arsenic, phosphorus adsorbent and preparation method thereof |
| CN109439376A (en) * | 2018-10-31 | 2019-03-08 | 沈阳三聚凯特催化剂有限公司 | A kind of ambient temperature desulfuration agent and preparation method thereof |
| EP4023329A4 (en) * | 2019-09-30 | 2022-11-23 | Rezel Catalysts Corporation | Dearsenification adsorbent and preparation method therefor |
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| CN107952409A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Sulphur, arsenic, phosphorus adsorbent and preparation method thereof |
| CN107952408A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Sulphur, arsenic, phosphorus cleanser and preparation method thereof |
| CN107952411A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Sulphur, arsenic, phosphorus cleanser and preparation method thereof |
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| CN107952411B (en) * | 2016-10-14 | 2020-02-07 | 中国石油化工股份有限公司 | Sulfur, arsenic and phosphorus purifying agent and preparation method thereof |
| CN109439376A (en) * | 2018-10-31 | 2019-03-08 | 沈阳三聚凯特催化剂有限公司 | A kind of ambient temperature desulfuration agent and preparation method thereof |
| EP4023329A4 (en) * | 2019-09-30 | 2022-11-23 | Rezel Catalysts Corporation | Dearsenification adsorbent and preparation method therefor |
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