CN107952408A - Sulphur, arsenic, phosphorus cleanser and preparation method thereof - Google Patents
Sulphur, arsenic, phosphorus cleanser and preparation method thereof Download PDFInfo
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- CN107952408A CN107952408A CN201610895785.2A CN201610895785A CN107952408A CN 107952408 A CN107952408 A CN 107952408A CN 201610895785 A CN201610895785 A CN 201610895785A CN 107952408 A CN107952408 A CN 107952408A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
Abstract
The present invention relates to a kind of sulphur, arsenic, phosphorus cleanser and preparation method thereof, mainly solves the problem of cleanser heap density in the prior art is high, and adsorption capacity is low.The present invention is by a kind of sulphur, arsenic, phosphorus cleanser, in terms of parts by weight, including following components:A) 1~10 part of aurichalcite;B) 10~50 parts of cupric oxide;C) 10~60 parts of zinc oxide;D) 0.1~10 part of nickel oxide;E) technical solution of 0.1~5 part of iron oxide preferably resolves the problem, in the purification available for natural gas, synthesis gas, lightweight liquid state hydro carbons etc..
Description
Technical field
The present invention relates to a kind of sulphur, arsenic, phosphorus cleanser and preparation method thereof.
Background technology
The impurity such as sulphur, arsenic, phosphorus are widely present in the raw materials such as natural gas, synthesis gas, coal gas, lightweight liquid state hydro carbons,
The presence of these impurity can cause many catalyst poisonings to inactivate, and greatly shorten catalyst life, even result in catalytic reaction without
Method is normally carried out;Can be as production be into being advanced into the composite of downstream, so as to bring a system in addition, not removing clean impurity
The problem of Environmental Health of row etc..Therefore, the impurity such as sulphur, arsenic, phosphorus are removed for protecting downstream unit high-efficiency high-accuracy
Major catalyst and the quality that improves downstream product at the same time have very important meaning.
Under normal circumstances, the sulphur-containing substance present in the raw material of industry is mainly H2S and COS, for these sulphur-containing substances
Deep removal effect most preferably Zinc oxide desulfurizer.Zinc oxide desulfurization with its desulfurization precision is high, easy to use, safe can
Lean on, sulfur capacity is high, plays " checking on " and " protection " acts on and occupy very important status, it be widely applied to synthesize ammonia,
The industries such as hydrogen manufacturing, coal chemical industry, petroleum refinement, beverage production, to remove natural gas, petroleum distillate, casing-head gas, refinery gas, synthesis
Hydrogen sulfide and some organic sulfurs in the raw materials such as gas, carbon dioxide.Sulphur in unstripped gas can be removed to by zinc sulphide desulfurization
0.055mg/kg.CuO is added in normal temp zinc oxide desulfuriging agent to improve its desulphurizing ability.It is de- that Zinc oxide desulfurizer is generally used for essence
Sulphur process, it can also absorb general organosulfur compound.Arsenic impurities in the raw material of industry, usually with AsH3Form exists, work
The Hydrodearsenic Catalyst used in industry is substantially divided into copper system, four class of lead system, manganese systems and nickel system, wherein relatively conventional with copper system.Copper system takes off
Arsenical arsenic holds height, can be carried out under room temperature, normal pressure and higher space velocity.Copper system Hydrodearsenic Catalyst is divided into metallic copper, CuO-Al again2O3、
CuO-ZnO-Al2O3Deng.When using CuO as active component, AsH3By Cu2+It is reduced at a low price or metallic state, arsenic is combined or swum with copper
From into element state.The development trend of desulfurizing agent and Hydrodearsenic Catalyst be to low bulk density, low temperature in use, high intensity and high sulfur capacity and
The direction that arsenic holds is developed.
Patent CN101591554A discloses a kind of normal temperature composite desulfurating and dearsenic agent and preparation method thereof, the desulfurating and dearsenic agent
It is made of carrier and active component, active component is lead oxide, magnetic iron oxide and cupric oxide, and carrier is γ-Al2O3, the desulfurization
Hydrodearsenic Catalyst needs, when 350~650 DEG C of activation 4~8 are small, to can be seen that the oxide desulfurization from its composition and preparation method and take off
Arsenical heap density is high, and preparation process is complicated, and commercial Application cost is higher.
Patent CN102049236A discloses a kind of copper zinc ambient temperature desulfuration agent and preparation method thereof, which is by alkali formula
Zinc carbonate, basic copper carbonate and binding agent composition, the preparation of the desulfurization sulfur agent is by commercially available basic zinc carbonate, basic carbonate
Copper, binding agent and water are mediated, are molded, being obtained after drying, which is obtained by physical mixed, thus zinc-copper therein
Active component can not play synergistic effect, so as to cause its Sulfur capacity relatively low.
Patent CN201410575030.5 discloses a kind of room temperature desulfurating and dearsenic agent and preparation method thereof, the desulfurating and dearsenic agent
It is made of aurichalcite, cupric oxide, zinc oxide and rare earth metal.The addition of rare earth metal improves the electric charge around Zn, Cu
Distribution, is conducive to the raising of its detergent power.
Patent CN201410314482.8 discloses a kind of sulphur arsenic adsorbent and preparation method thereof, which is by green
Copper zinc ore, cupric oxide, zinc oxide, iron oxide, manganese oxide composition.The addition of iron oxide, manganese oxide improves the Sulfur capacity of adsorbent
Hold with arsenic.
Although such scheme makes moderate progress and improves to the adsorption capacity of adsorbent.But, however it remains cleanser heap is close
The problem of degree is high, and adsorption capacity is low, it is especially low to the adsorption capacity of phosphorus.
The content of the invention
The technical problems to be solved by the invention are the problem of cleanser heap density are high, and adsorption capacity is low in the prior art,
A kind of new sulphur, arsenic, phosphorus cleanser and preparation method thereof are provided.The sulphur, arsenic, phosphorus cleanser contain aurichalcite and CuO-ZnO
Class solid solution, while nickel oxide is introduced, boehmite is added in precipitation process, improves the detergent power of cleanser, is had
There is the advantages of heap density is low, and adsorption capacity is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:By a kind of sulphur, arsenic, phosphorus cleanser, with
Parts by weight meter, including following components:A) 1~10 part of aurichalcite;B) 10~50 parts of cupric oxide;C) 10~60 parts of oxygen
Change zinc;D) 0.1~10 part of nickel oxide;E) 0.1~5 part of iron oxide.
In above-mentioned technical proposal, in terms of sulphur, arsenic, phosphorus cleanser parts by weight, the preferred scope of the aurichalcite for 2~
8 parts;The preferred scope of the cupric oxide is 13~48;The preferred scope of the zinc oxide zinc is 15~55 parts;The nickel oxide
Content be 1~8 part;The content of the iron oxide is 1~4 part.Sulphur, arsenic, phosphorus cleanser heap density are less than 1.0kg/m3, side pressure
Intensity is more than 70N/.
The room temperature sulphur, arsenic, the preparation method of phosphorus cleanser, in turn include the following steps:
(1) by Gerhardite, zinc nitrate hexahydrate, ferric nitrate, Nickelous nitrate hexahydrate and hydromassage, your ratio is counted:Cu/
Zn is 0.1~2;(Fe+Ni)/(Cu+Zn) is 0.01~0.25;Fe/Ni is 0.25~1;(Cu+Zn+Fe+Ni)/H2O is 0.01
~0.04 ratio mixing, stirs evenly to obtain solution I;
(2) by least one of sodium carbonate, sodium acid carbonate, ammonium carbonate and hydromassage that than the ratio for 0.01~0.04
Mixing, stirs evenly to obtain solution II;
(3) solution I and II is uniformly mixed, at 40~90 DEG C, when reaction 0.5~3 is small;
(4) boehmite is added into mixed solution, when reaction 0.25~1 is small, filtration washing sediment is molten after washing
The electrical conductivity of liquid is not more than 100 μ s/cm;
(5) sediment, mix lubricant are rolled to the water for uniformly adding 10~50 weight %, are granulated;
(6) by the powder being granulated at 170~300 DEG C, when roasting 1~5 is small;
(7) compression molding is sulphur, arsenic, phosphorus cleanser.
In above-mentioned technical proposal, the water added in step (5) is on the basis of the gross weight of sediment and lubricant;
The lubricant is at least one of graphite, talcum powder, sesbania powder and stearic acid.
Room temperature sulphur of the present invention, arsenic, phosphorus cleanser, due to containing aurichalcite, its volume is larger, in banking process
Larger duct can be produced, thus its heap density is relatively low.The CuO-ZnO class solid solution formed after aurichalcite heat treatment, such
Arrange more ZnO in solid solution around CuO, and similarly, also arranged more CuO around ZnO, it is ensured that CuO and ZnO are abundant
Refinement so that the chance of CuO particles and ZnO particle interracial contact greatly increases, there is provided more activated centres.The sulphur, arsenic, phosphorus
Cleanser introduces nickel oxide, and nickel oxide interacts with cupric oxide, zinc oxide and iron oxide, improves the electric charge point in activated centre
Cloth so that sulphur, arsenic, the adsorption capacity of phosphorus cleanser improve, and have been improved particularly the adsorption capacity of phosphorus.Introduced in coprecipitation process
Boehmite, further increases the dispersiveness in activated centre, so that the adsorption capacity of sulphur, arsenic, phosphorus cleanser is into one
Step improves.The present invention achieves preferable technique effect.
Room temperature sulphur of the present invention, arsenic, phosphorus cleanser can be used for the net of natural gas, synthesis gas, lightweight liquid state hydro carbons etc.
In change.In room temperature, normal pressure, volume space velocity 3000h-1Under conditions of, with sulphur containing various concentrations, arsenic, phosphorus compound impurity nitrogen
Gas or synthesis gas are by reactor, and the adsorption capacity of adsorbent is up to more than 20%.It is empty in room temperature, pressure 3.0MPa, quality
Speed is 3.5h-1Under conditions of, with sulphur containing various concentrations, arsenic, phosphorus compound impurity propylene liguid by reactor, adsorbent
Adsorption capacity is also up to more than 20%.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Comparative example 1】
By 500 kilograms of 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 10 kilograms of ANN aluminium nitrate nonahydrate and water
It is mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water is uniformly mixed and obtains sodium carbonate liquor, will
Sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, sediment is washed drying, then adds 6 kilograms
Aluminium oxide, 1 kilogram of graphite mixing roll, then add the water of 30 weight %, be granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains
1 is shown in Table to sample composition.
【Comparative example 2】
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 10 kilograms of ANN aluminium nitrate nonahydrate, ferric nitrate 2,000
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, and when 70 DEG C of reactions 1 are small, sediment is washed drying,
6 kilograms of aluminium oxide are then added, 1 kilogram of graphite mixing rolls, then adds the water of 30 weight %, be granulated, and 270 DEG C of roastings 2 are small
When, compression molding, obtains sample composition and is shown in Table 1.
【Comparative example 3】
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 10 kilograms of ANN aluminium nitrate nonahydrate, six nitric hydrates
500 kilograms of 2.5 kilograms of nickel and water are mixed evenly to obtain metal salt solution, by the 550 kilograms of mixing of 30 kilograms of sodium carbonate and water
Sodium carbonate liquor uniformly is obtained, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, by sediment
Drying is washed, then adds 6 kilograms of aluminium oxide, 1 kilogram of graphite mixing rolls, then adds the water of 30 weight %, be granulated, 270
DEG C roasting 2 it is small when, compression molding, obtains sample composition and is shown in Table 1.
【Comparative example 4】
4 synthetic sample of comparative example is oxidation iron nickel oxide
By 40 kilograms of ferric nitrate, 300 kilograms of 28 kilograms of nickel nitrate and water are mixed evenly to obtain metal salt solution, by carbon
350 kilograms of 20 kilograms of sour sodium and water are uniformly mixed and obtain sodium carbonate liquor, and sodium carbonate liquor is uniformly mixed with metal salt solution,
When 70 DEG C of reactions 1 are small, sediment is washed into drying, adds 6 kilograms of aluminium oxide, 1 kilogram of graphite mixing rolls, and then adds 30
The water of weight %, is granulated, and when 350 DEG C of roastings 5 are small, compression molding, obtains sample composition and be shown in Table 1.
【Comparative example 5】
Boehmite is added in granulation process compared with Example 1.
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 2 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 2.5 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, and when 70 DEG C of reactions 1 are small, sediment is washed drying,
Then the water mixing of 5 kilograms, 1 kilogram graphite of addition boehmite, 30 weight % rolls, and is granulated, when 270 DEG C of roastings 2 are small, pressure
Sheetmolding, obtains sample composition and is shown in Table 1.
【Embodiment 1】
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 2 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 2.5 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, adds boehmite 5,000
Gram, when reaction 0.5 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1,000
The water mixing of gram graphite, 30 weight % rolls, and is granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 2】
By 20 kilograms of Gerhardite, 50 kilograms of zinc nitrate hexahydrate, 2 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 2.5 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 60 DEG C of reactions 2 are small, adds boehmite 5,000
Gram, when reaction 0.5 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1,000
The water mixing of gram graphite, 35 weight % rolls, and is granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 3】
By 10 kilograms of Gerhardite, 60 kilograms of zinc nitrate hexahydrate, 2 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 2.5 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 60 DEG C of reactions 2 are small, adds boehmite 6,000
Gram, when reaction 0.5 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1,000
The water mixing of gram graphite, 35 weight % rolls, and is granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 4】
By 40 kilograms of Gerhardite, 30 kilograms of zinc nitrate hexahydrate, 2 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 2.5 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 26 kilograms of ammonium carbonate and water are uniformly mixed and obtained
Sal volatile, sal volatile is uniformly mixed with metal salt solution, when 80 DEG C of reactions 1 are small, adds boehmite 6,000
Gram, when reaction 1 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1 kilogram
The water mixing of graphite, 40 weight % rolls, and is granulated, and when 250 DEG C of roastings 5 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 5】
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 1 kilogram of ferric nitrate, Nickelous nitrate hexahydrate 1.3 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, adds boehmite 5,000
Gram, when reaction 0.5 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1,000
The water mixing of gram graphite, 30 weight % rolls, and is granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 6】
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 3 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 3.9 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, adds boehmite 5,000
Gram, when reaction 0.5 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1,000
The water mixing of gram graphite, 30 weight % rolls, and is granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 7】
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 4 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 5.2 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, adds boehmite 5,000
Gram, when reaction 0.5 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1,000
The water mixing of gram graphite, 30 weight % rolls, and is granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 8】
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 5 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 7.5 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, adds boehmite 5,000
Gram, when reaction 0.5 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1,000
The water mixing of gram graphite, 30 weight % rolls, and is granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 9】
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 0.1 kilogram of ferric nitrate, Nickelous nitrate hexahydrate
0.25 kilogram is mixed evenly to obtain metal salt solution with 500 kilograms of water, and 30 kilograms of sodium carbonate and 550 kilograms of mixing of water is equal
It is even to obtain sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, add and intends thin water
5 kilograms of aluminium stone, when reaction 0.5 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, and then
The water mixing of 1 kilogram of graphite of addition, 30 weight % rolls, and is granulated, and when 280 DEG C of roastings 2 are small, compression molding, obtains sample composition
It is shown in Table 1.
【Embodiment 10】
By 30 kilograms of Gerhardite, 40 kilograms of zinc nitrate hexahydrate, 2 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 12.5
Kilogram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed
To sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, adds boehmite 5
Kilogram, when reaction 0.5 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1
The water mixing of kilogram graphite, 30 weight % rolls, and is granulated, and when 290 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 11】
By 6 kilograms of Gerhardite, 8 kilograms of zinc nitrate hexahydrate, 2 kilograms of ferric nitrate, 10 kilograms of Nickelous nitrate hexahydrate
It is mixed evenly to obtain metal salt solution with water double centner, 110 kilograms of 6 kilograms of sodium carbonate and water is uniformly mixed and obtains carbon
Acid sodium solution, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, adds boehmite 1,000
Gram, when reaction 1 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 0.2 thousand
The water mixing of gram graphite, 30 weight % rolls, and is granulated, and when 300 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 12】
By 60 kilograms of Gerhardite, 10 kilograms of zinc nitrate hexahydrate, 2 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 7.5 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, adds boehmite 6,000
Gram, when reaction 1 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1 kilogram
The water mixing of graphite, 30 weight % rolls, and is granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
【Embodiment 13】
By 50 kilograms of Gerhardite, 20 kilograms of zinc nitrate hexahydrate, 2 kilograms of ferric nitrate, Nickelous nitrate hexahydrate 2.5 thousand
Gram and 500 kilograms of water be mixed evenly to obtain metal salt solution, 550 kilograms of 30 kilograms of sodium carbonate and water are uniformly mixed and obtained
Sodium carbonate liquor, sodium carbonate liquor is uniformly mixed with metal salt solution, when 70 DEG C of reactions 1 are small, adds boehmite 6,000
Gram, when reaction 0.25 is small, sediment is washed, until filtrate electrical conductivity is less than 100 μ s/cm, drying precipitate, then adds 1
The water mixing of kilogram graphite, 30 weight % rolls, and is granulated, and when 270 DEG C of roastings 2 are small, compression molding, obtains sample composition and be shown in Table 1.
Table 1
【Embodiment 14】
Sulphur, arsenic, phosphorus cleanser prepared by above-described embodiment are ground into the particle of 20~40 mesh, and filling it into internal diameter is
In the reactor of 1cm, in room temperature, normal pressure, volume space velocity 3000h-1Under conditions of, with sulphur containing various concentrations, arsenic, phosphorus compound
The nitrogen of impurity is evaluated the sulphur, arsenic, phosphorus cleanser, the results are shown in Table 2 by the reactor.
Table 2
【Embodiment 15】
Sulphur, arsenic, phosphorus cleanser prepared by above-described embodiment are ground into the particle of 20~40 mesh, and filling it into internal diameter is
In the reactor of 1cm, in room temperature, normal pressure, volume space velocity 3000h-1Under conditions of, with sulphur containing various concentrations, arsenic, phosphorus compound
The synthesis gas of impurity is evaluated the sulphur, arsenic, phosphorus cleanser, the results are shown in Table 3 by the reactor.
Table 3
【Embodiment 16】
Sulphur, arsenic, phosphorus cleanser prepared by above-described embodiment are ground into the particle of 20~40 mesh, and filling it into internal diameter is
In the reactor of 1cm, in room temperature, pressure 3.0MPa, mass space velocity 3.5h-1Under conditions of, with sulphur containing various concentrations, arsenic, phosphorus
The propylene liguid of compound impurities is evaluated the sulphur, arsenic, phosphorus cleanser, the results are shown in Table 4 by the reactor.
Table 4
Claims (10)
1. a kind of sulphur, arsenic, phosphorus cleanser, in terms of parts by weight, including following components:
A) 1~10 part of aurichalcite;
B) 10~50 parts of cupric oxide;
C) 10~60 parts of zinc oxide;
D) 0.1~10 part of nickel oxide;
E) 0.1~5 part of iron oxide.
2. sulphur, arsenic, phosphorus cleanser according to claim 1, it is characterised in that green in terms of sulphur, arsenic, phosphorus cleanser parts by weight
Copper zinc ore content is 2~8 parts.
3. sulphur, arsenic, phosphorus cleanser according to claim 1, it is characterised in that in terms of sulphur, arsenic, phosphorus cleanser parts by weight, oxygen
It is 13~48 parts to change copper content.
4. sulphur, arsenic, phosphorus cleanser according to claim 1, it is characterised in that in terms of sulphur, arsenic, phosphorus cleanser parts by weight, oxygen
It is 15~55 parts to change Zn content.
5. sulphur, arsenic, phosphorus cleanser according to claim 1, it is characterised in that in terms of sulphur, arsenic, phosphorus cleanser parts by weight, oxygen
The content for changing nickel is 1~8 part.
6. sulphur, arsenic, phosphorus cleanser according to claim 1, it is characterised in that in terms of sulphur, arsenic, phosphorus cleanser parts by weight, oxygen
The content for changing iron is 1~4 part.
7. sulphur, arsenic, phosphorus cleanser according to claim 1, it is characterised in that sulphur, arsenic, the heap density of phosphorus cleanser are less than
1.0kg/m3, side pressure strength is more than 70N/.
8. claim 1~7 any one of them sulphur, arsenic, the preparation method of phosphorus cleanser, comprise the following steps successively:
(1) by Gerhardite, zinc nitrate hexahydrate, ferric nitrate, Nickelous nitrate hexahydrate and hydromassage, your ratio is counted:Cu/Zn is
0.1~2;(Fe+Ni)/(Cu+Zn) is 0.01~0.25;Fe/Ni is 0.25~1;(Cu+Zn+Fe+Ni)/H2O for 0.01~
0.04 ratio mixing, stirs evenly to obtain solution I;
(2) by least one of sodium carbonate, sodium acid carbonate, ammonium carbonate and hydromassage that than being mixed for 0.01~0.04 ratio
Close, stir evenly to obtain solution II;
(3) solution I and II is uniformly mixed, at 40~90 DEG C, when reaction 0.5~3 is small;
(4) boehmite is added into mixed solution, when reaction 0.25~1 is small, filtration washing sediment, solution after washing
Electrical conductivity is not more than 100 μ s/cm;
(5) sediment, mix lubricant are rolled to the water for uniformly adding 10~50 weight %, are granulated;
(6) by the powder being granulated at 170~300 DEG C, when roasting 1~5 is small;
(7) compression molding is sulphur, arsenic, phosphorus cleanser.
9. the preparation method of sulphur arsenic cleanser according to claim 8, it is characterised in that lubricant for graphite, talcum powder,
At least one of sesbania powder and stearic acid.
10. claim 1~9 any one of them sulphur, arsenic, phosphorus cleanser are used for natural gas, synthesis gas, lightweight liquid state hydrocarbon
In the purification of class.
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CN113522233A (en) * | 2020-04-17 | 2021-10-22 | 中国石油化工股份有限公司 | Purifying agent, preparation method and application thereof, and purifying method |
CN113522233B (en) * | 2020-04-17 | 2023-09-29 | 中国石油化工股份有限公司 | Purifying agent, preparation method and application thereof and purifying method |
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