CN107952411B - Sulfur, arsenic and phosphorus purifying agent and preparation method thereof - Google Patents
Sulfur, arsenic and phosphorus purifying agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sulfur, arsenic and phosphorus purifying agent and a preparation method thereof, and mainly solves the problems of high bulk density and low adsorption capacity of the purifying agent in the prior art. The invention relates to a sulfur, arsenic and phosphorus purifying agent, which comprises the following components in parts by weight: a) 1-10 parts of green copper zinc ore; b) 10-50 parts of copper oxide; c) 10-60 parts of zinc oxide; d) 0.1-10 parts of nickel oxide; e) the technical scheme of 0.1-5 parts of manganese oxide well solves the problem, and can be used for purifying natural gas, synthetic gas, light gas liquid hydrocarbons and the like.
Description
Technical Field
The invention relates to a sulfur, arsenic and phosphorus purifying agent and a preparation method thereof.
Background
The impurities such as sulfur, arsenic, phosphorus and the like widely exist in natural gas, synthesis gas, coal gas, light gas liquid hydrocarbon and other raw materials, and the existence of the impurities can cause poisoning and inactivation of a plurality of catalysts, greatly shorten the service life of the catalysts and even cause that the catalytic reaction cannot be normally carried out; in addition, impurities which are not removed cleanly enter downstream synthetics along with the production, so that a series of problems in aspects of environmental health and the like are caused. Therefore, the efficient and accurate removal of impurities such as sulfur, arsenic, and phosphorus is very important for protecting the main catalyst of the downstream equipment and improving the quality of the downstream product.
In general, the sulfur species present in industrial feedstocks are primarily H2S and COS, the best effect for deeply removing the sulfur-containing substances is a zinc oxide desulfurizer. The zinc oxide desulfurization has high desulfurization precision, convenient use, stability, reliability and high sulfur capacity, plays a role of 'gate' and 'protection', occupies a very important position, and is widely applied to the industries of ammonia synthesis, hydrogen production, coal chemical industry, petroleum refining, beverage production and the like to remove hydrogen sulfide and certain organic sulfur in raw materials such as natural gas, petroleum fractions, oil field gas, refinery gas, synthesis gas, carbon dioxide and the like. The desulfurization of the zinc sulfide can remove the sulfur in the feed gas to 0.055 mg/kg. CuO is added into the normal-temperature zinc oxide desulfurizer to improve the desulfurization capability of the zinc oxide desulfurizer. The zinc oxide desulfurizing agent is generally used in fine desulfurization, and it can also absorb general organic sulfur compounds. Arsenic impurities in industrial feedstocks, in generalWith AsH3As the dearsenization agent used in industry, it can be roughly classified into copper, lead, manganese and nickel, among which copper is more common. The copper-based dearsenization agent has high arsenic capacity and can be carried out at normal temperature, normal pressure and high airspeed. The copper-based dearsenization agent can be further divided into metallic copper and CuO-Al2O3、CuO-ZnO-Al2O3And the like. When CuO is used as an active component, AsH3Mixing Cu2+Reduced to a low valence or metallic state, and arsenic is bound to copper or dissociated to an elemental state. The trend in the development of desulfurizing and dearsenizing agents is toward lower bulk density, lower use temperature, higher strength, and higher sulfur and arsenic capacities.
The patent CN101591554A discloses a normal temperature composite desulfuration and dearsenization agent and a preparation method thereof, the desulfuration and dearsenization agent consists of a carrier and active components, the active components comprise lead oxide, magnetic manganese oxide and copper oxide, and the carrier is gamma-Al2O3The desulfurization and dearsenization agent needs to be activated for 4-8 hours at 350-650 ℃, and the composition and the preparation method show that the oxide desulfurization and dearsenization agent has high bulk density, complex preparation process and higher industrial application cost.
Patent CN102049236A discloses a copper-zinc normal temperature desulfurizer and a preparation method thereof, the desulfurizer consists of basic zinc carbonate, basic copper carbonate and a binder, the preparation of the sulfur-removing agent is obtained by kneading, molding and drying the commercially available basic zinc carbonate, basic copper carbonate, the binder and water, and the desulfurizer is obtained by physical mixing, so that the active components of zinc and copper in the desulfurizer can not play a synergistic effect, thereby leading the sulfur capacity of the desulfurizer to be lower.
Patent CN201410575030.5 discloses a normal temperature desulfurization and dearsenization agent and a preparation method thereof, wherein the desulfurization and dearsenization agent is composed of auricuprite, copper oxide, zinc oxide and rare earth metal. The addition of rare earth metal improves the charge distribution around Zn and Cu, and is beneficial to improving the purification capacity of the alloy.
Patent CN201410314482.8 discloses a sulfur-arsenic adsorbent and its preparation method, wherein the adsorbent is composed of aurichalcite, copper oxide, zinc oxide, iron oxide, and manganese oxide. The addition of ferric oxide and manganese oxide improves the sulfur capacity and arsenic capacity of the adsorbent.
The scheme improves and enhances the adsorption capacity of the adsorbent. However, there are still problems that the bulk density of the scavenger is high and the adsorption capacity is low, particularly the adsorption capacity for phosphorus is low.
Disclosure of Invention
The invention aims to solve the technical problems of high bulk density and low adsorption capacity of a purifying agent in the prior art, and provides a novel sulfur, arsenic and phosphorus purifying agent and a preparation method thereof. The sulfur, arsenic and phosphorus purifying agent contains the auricuprite and CuO-ZnO solid solution, nickel oxide is introduced, and pseudo-boehmite is added in the precipitation process, so that the purifying capacity of the purifying agent is improved, and the purifying agent has the advantages of low bulk density and high adsorption capacity.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the sulfur, arsenic and phosphorus purifying agent comprises the following components in parts by weight: a) 1-10 parts of green copper zinc ore; b) 10-50 parts of copper oxide; c) 10-60 parts of zinc oxide; d) 0.1-10 parts of nickel oxide; e) 0.1-5 parts of manganese oxide.
In the technical scheme, the preferable range of the aurichalcite is 2-8 parts by weight of sulfur, arsenic and phosphorus purificant; the preferable range of the copper oxide is 13-48; the preferable range of the zinc oxide is 15-55 parts; the content of the nickel oxide is 1-8 parts; the content of the manganese oxide is 1-4 parts. The bulk density of the sulfur, arsenic and phosphorus purifying agent is less than 1.0kg/m3The lateral pressure intensity is more than 70N/grain.
The preparation method of the normal-temperature sulfur, arsenic and phosphorus purifying agent sequentially comprises the following steps:
(1) calculating copper nitrate trihydrate, zinc nitrate hexahydrate, a 50% aqueous solution of manganese nitrate, nickel nitrate hexahydrate and water according to a molar ratio: Cu/Zn is 0.1-2; the (Fe + Ni)/(Cu + Zn) is 0.01-0.25; Fe/Ni is 0.25-1; (Cu + Zn + Fe + Ni)/H2Mixing O in a proportion of 0.01-0.04, and uniformly stirring to obtain a solution I;
(2) mixing at least one of sodium carbonate, sodium bicarbonate and ammonium carbonate with water according to a molar ratio of 0.01-0.04, and uniformly stirring to obtain a solution II;
(3) uniformly mixing the solution I and the solution II, and reacting for 0.5-3 hours at 40-90 ℃;
(4) adding pseudo-boehmite into the mixed solution, reacting for 0.25-1 hour, filtering and washing the precipitate, wherein the conductivity of the washed solution is not more than 100 mus/cm;
(5) mixing and rolling the precipitate and the lubricant uniformly, adding 10-50 wt% of water, and granulating;
(6) roasting the granulated powder for 1-5 hours at 170-300 ℃;
(7) tabletting and forming into the sulfur, arsenic and phosphorus purifying agent.
In the technical scheme, the water amount added in the step (5) is based on the total weight of the precipitate and the lubricant; the lubricant is at least one of graphite, talcum powder, sesbania powder and stearic acid.
The normal temperature sulfur, arsenic and phosphorus purifying agent of the invention contains the green copper zinc ore, has larger volume, and can generate larger pore canals in the stacking process, so the bulk density is lower. In the CuO-ZnO solid solution formed after the heat treatment of the aurite-cuprite, more ZnO is distributed around the CuO in the solid solution, and similarly, more CuO is also distributed around the ZnO, so that the CuO and the ZnO can be ensured to be fully refined, the chance of the contact between the CuO particles and the ZnO particles is greatly increased, and more active centers are provided. The sulfur, arsenic and phosphorus purifying agent introduces nickel oxide, the nickel oxide interacts with copper oxide, zinc oxide and manganese oxide, the charge distribution of an active center is improved, the adsorption capacity of the sulfur, arsenic and phosphorus purifying agent is improved, and pseudo-boehmite is further introduced in the coprecipitation process, so that the dispersibility of the active center is greatly improved, the adsorption capacity of the sulfur, arsenic and phosphorus purifying agent is improved, and especially the adsorption capacity of phosphorus is improved. The invention achieves better technical effect.
The normal temperature sulfur, arsenic and phosphorus purifying agent can be used for purifying natural gas, synthetic gas, light gas liquid hydrocarbon and the like. At normal temperature and pressure and volume airspeed of 3000h-1Under the condition of (1), nitrogen or synthesis gas containing sulfur, arsenic and phosphorus compound impurities with different concentrations passes through the reactor, and the adsorption capacity of the adsorbent can reach more than 20%.At normal temperature, the pressure is 3.0MPa, and the mass space velocity is 3.5h-1Under the condition, liquid propylene containing sulfur, arsenic and phosphorus compound impurities with different concentrations passes through the reactor, and the adsorption capacity of the adsorbent can also reach more than 20 percent.
The invention is further illustrated by the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE 1 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted for 1 hour at 70 ℃, precipitates are washed and dried, then 6 kg of aluminum oxide and 1 kg of graphite are added, the mixture is mixed and rolled, then 30 wt% of water is added, the mixture is granulated, roasted for 2 hours at 270 ℃, and the mixture is tabletted and molded to obtain a sample composition shown in table 1.
[ COMPARATIVE EXAMPLE 2 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, precipitates are washed and dried, then 6 kg of aluminum oxide and 1 kg of graphite are added, the mixture is mixed and rolled, then 30% by weight of water is added, granulation is carried out, roasting is carried out at 270 ℃ for 2 hours, and tabletting molding is carried out, so that the composition of a sample is shown in table 1.
[ COMPARATIVE EXAMPLE 3 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 10 kg of aluminum nitrate nonahydrate, 2.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, precipitates are washed and dried, then 6 kg of aluminum oxide and 1 kg of graphite are added for mixing and rolling, then 30 wt% of water is added, granulation is carried out, roasting is carried out at 270 ℃ for 2 hours, and tabletting molding is carried out, so that the composition of a sample is shown in table 1.
[ COMPARATIVE EXAMPLE 4 ]
Comparative example 4 the synthesized sample was manganese oxide nickel oxide
Mixing and stirring 70 kg of manganese nitrate 50% aqueous solution, 28 kg of nickel nitrate and 300 kg of water uniformly to obtain metal salt solution, mixing 20 kg of sodium carbonate and 350 kg of water uniformly to obtain sodium carbonate solution, mixing the sodium carbonate solution and the metal salt solution uniformly, reacting at 70 ℃ for 1 hour, washing and drying the precipitate, adding 6 kg of alumina and 1 kg of graphite, mixing and rolling, adding 30 wt% of water, granulating, roasting at 350 ℃ for 5 hours, and tabletting to obtain the sample composition shown in table 1.
[ COMPARATIVE EXAMPLE 5 ]
Compared to example 1, pseudo-boehmite was added during granulation.
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate, 2.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, precipitates are washed and dried, 5 kg of pseudo-boehmite, 1 kg of graphite and 30 wt% of water are added, the mixture is rolled and ground, granulation is carried out, roasting is carried out at 270 ℃ for 2 hours, and tabletting forming is carried out, so that the composition of a sample is shown in table 1.
[ example 1 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate, 2.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, 5 kg of pseudo-boehmite is added, the reaction is carried out for 0.5 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 30 wt% of water are added, the mixture is rolled, and the mixture is granulated, roasted at 270 ℃ for 2 hours, and tabletted and molded to obtain a sample composition shown in Table 1.
[ example 2 ]
20 kg of copper nitrate trihydrate, 50 kg of zinc nitrate hexahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate, 2.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 60 ℃ for 2 hours, 5 kg of pseudo-boehmite is added, the reaction is carried out for 0.5 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 35 wt% of water are added, the mixture is rolled, and the mixture is granulated, roasted at 270 ℃ for 2 hours, and tabletted and molded to obtain a sample composition shown in Table 1.
[ example 3 ]
10 kg of copper nitrate trihydrate, 60 kg of zinc nitrate hexahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate, 2.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 60 ℃ for 2 hours, 6 kg of pseudo-boehmite is added, the reaction is carried out for 0.5 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 35 wt% of water are added, the mixture is rolled, and the mixture is granulated, roasted at 270 ℃ for 2 hours, and tabletted and molded to obtain a sample composition shown in Table 1.
[ example 4 ]
40 kg of copper nitrate trihydrate, 30 kg of zinc nitrate hexahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate, 2.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 26 kg of ammonium carbonate and 550 kg of water are mixed uniformly to obtain an ammonium carbonate solution, the ammonium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 80 ℃ for 1 hour, 6 kg of pseudo-boehmite is added, the reaction is carried out for 1 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 40 wt% of water are added, mixed, rolled, granulated, roasted at 250 ℃ for 5 hours, and tabletted and molded to obtain a sample composition shown in table 1.
[ example 5 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 1.7 kg of a 50% aqueous solution of manganese nitrate, 1.3 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, 5 kg of pseudo-boehmite is added, the reaction is carried out for 0.5 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 30 wt% of water are added, the mixture is rolled, and the mixture is granulated, roasted at 270 ℃ for 2 hours, and tabletted and molded to obtain a sample composition shown in Table 1.
[ example 6 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 5.1 kg of a 50% aqueous solution of manganese nitrate, 3.9 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, 5 kg of pseudo-boehmite is added, the reaction is carried out for 0.5 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 30 wt% of water are added, the mixture is rolled, and the mixture is granulated, roasted at 270 ℃ for 2 hours, and tabletted and molded to obtain a sample composition shown in Table 1.
[ example 7 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 6.8 kg of a 50% aqueous solution of manganese nitrate, 5.2 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, 5 kg of pseudo-boehmite is added, the reaction is carried out for 0.5 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 30 wt% of water are added, the mixture is rolled, and the mixture is granulated, roasted at 270 ℃ for 2 hours, and tabletted and molded to obtain a sample composition shown in Table 1.
[ example 8 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 8.5 kg of a 50% aqueous solution of manganese nitrate, 7.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, 5 kg of pseudo-boehmite is added, the reaction is carried out for 0.5 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 30 wt% of water are added, the mixture is rolled, and the mixture is granulated, roasted at 270 ℃ for 2 hours, and tabletted and molded to obtain a sample composition shown in Table 1.
[ example 9 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 0.2 kg of a 50% aqueous solution of manganese nitrate, 0.25 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted for 1 hour at 70 ℃, 5 kg of pseudo-boehmite is added, the reaction is carried out for 0.5 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 30 wt% of water are added, the mixture is rolled, granulated, roasted for 2 hours at 280 ℃, and the mixture is tabletted and molded to obtain a sample composition shown in table 1.
[ example 10 ]
30 kg of copper nitrate trihydrate, 40 kg of zinc nitrate hexahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate, 12.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, 5 kg of pseudo-boehmite is added, the reaction is carried out for 0.5 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 30 wt% of water are added, the mixture is rolled, and the mixture is granulated, roasted at 290 ℃ for 2 hours, and tabletted and molded to obtain a sample composition shown in Table 1.
[ example 11 ]
6 kg of copper nitrate trihydrate, 8 kg of zinc nitrate hexahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate, 10 kg of nickel nitrate hexahydrate and 100 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 6 kg of sodium carbonate and 110 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted for 1 hour at 70 ℃, 1 kg of pseudo-boehmite is added, the reaction is carried out for 1 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 0.2 kg of graphite and 30 wt% of water are added, the mixture is mixed, rolled, granulated, roasted for 2 hours at 300 ℃, and tabletted and molded to obtain a sample composition shown in table 1.
[ example 12 ]
60 kg of copper nitrate trihydrate, 10 kg of zinc nitrate hexahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate, 7.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, 6 kg of pseudo-boehmite is added, the reaction is carried out for 1 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 30 wt% of water are added, the mixture is rolled, granulated, roasted at 270 ℃ for 2 hours, and the mixture is tabletted and molded to obtain a sample composition shown in Table 1.
[ example 13 ]
50 kg of copper nitrate trihydrate, 20 kg of zinc nitrate hexahydrate, 3.4 kg of a 50% aqueous solution of manganese nitrate, 2.5 kg of nickel nitrate hexahydrate and 500 kg of water are mixed and stirred uniformly to obtain a metal salt solution, 30 kg of sodium carbonate and 550 kg of water are mixed uniformly to obtain a sodium carbonate solution, the sodium carbonate solution and the metal salt solution are mixed uniformly, the mixture is reacted at 70 ℃ for 1 hour, 6 kg of pseudo-boehmite is added, the reaction is carried out for 0.25 hour, precipitates are washed until the conductivity of filtrate is less than 100 mu s/cm, the precipitates are dried, then 1 kg of graphite and 30 wt% of water are added, the mixture is rolled, and the mixture is granulated, roasted at 270 ℃ for 2 hours, and tabletted and molded to obtain a sample composition shown in Table 1.
TABLE 1
[ example 14 ]
The sulfur, arsenic and phosphorus purifying agents prepared in the embodiments are crushed into 20-40 mesh particles, and the particles are filled into a reactor with the inner diameter of 1cm at normal temperature and normal pressure and with the volume space velocity of 3000h-1The sulfur, arsenic and phosphorus scavengers were evaluated by passing nitrogen gas containing various concentrations of sulfur, arsenic and phosphorus impurities through the reactor, and the results are shown in Table 2.
TABLE 2
[ example 15 ]
The sulfur, arsenic and phosphorus purifying agents prepared in the embodiments are crushed into 20-40 mesh particles, and the particles are filled into a reactor with the inner diameter of 1cm at normal temperature and normal pressure and with the volume space velocity of 3000h-1The sulfur, arsenic and phosphorus scavengers were evaluated by passing synthesis gas containing various concentrations of sulfur, arsenic and phosphorus impurities through the reactor, and the results are shown in table 3.
TABLE 3
[ example 16 ]
The sulfur, arsenic and phosphorus purifying agent prepared in the above embodimentCrushing into 20-40 mesh particles, filling the particles into a reactor with the inner diameter of 1cm, and keeping the pressure at 3.0MPa and the mass space velocity at 3.5h at normal temperature-1The sulfur, arsenic and phosphorus scavengers were evaluated by passing liquid propylene containing various concentrations of sulfur, arsenic and phosphorus impurities through the reactor, and the results are shown in Table 4.
TABLE 4
Claims (9)
1. A sulfur, arsenic and phosphorus purifying agent comprises the following components in parts by weight:
a) 1-10 parts of green copper zinc ore;
b) 10-50 parts of copper oxide;
c) 10-60 parts of zinc oxide;
d) 0.1-10 parts of nickel oxide;
e) 0.1-5 parts of manganese oxide;
the preparation method of the sulfur, arsenic and phosphorus purifying agent sequentially comprises the following steps:
(1) calculating copper nitrate trihydrate, zinc nitrate hexahydrate, a 50% aqueous solution of manganese nitrate, nickel nitrate hexahydrate and water according to a molar ratio: Cu/Zn is 0.1-2; (Mn + Ni)/(Cu + Zn) is 0.01-0.25; Mn/Ni is 0.25-1; (Cu + Zn + Mn + Ni)/H2Mixing O in a proportion of 0.01-0.04, and uniformly stirring to obtain a solution I;
(2) mixing at least one of sodium carbonate, sodium bicarbonate and ammonium carbonate with water according to a molar ratio of 0.01-0.04, and uniformly stirring to obtain a solution II;
(3) uniformly mixing the solution I and the solution II, and reacting for 0.5-3 hours at 40-90 ℃;
(4) adding pseudo-boehmite into the mixed solution, reacting for 0.25-1 hour, filtering and washing the precipitate, wherein the conductivity of the washed solution is not more than 100 mus/cm;
(5) mixing and rolling the precipitate and the lubricant uniformly, adding 10-50 wt% of water, and granulating;
(6) roasting the granulated powder for 1-5 hours at 170-300 ℃;
(7) tabletting and forming into the sulfur, arsenic and phosphorus purifying agent.
2. The sulfur, arsenic and phosphorus purifying agent as claimed in claim 1, wherein the content of the aurichalcite is 2-8 parts by weight of the sulfur, arsenic and phosphorus purifying agent.
3. The sulfur, arsenic and phosphorus purifying agent as claimed in claim 1, wherein the content of copper oxide is 13-48 parts by weight of the sulfur, arsenic and phosphorus purifying agent.
4. The sulfur, arsenic and phosphorus purifying agent as claimed in claim 1, wherein the zinc oxide is 15-55 weight portions.
5. The sulfur, arsenic and phosphorus purifying agent as defined in claim 1, wherein the content of nickel oxide is 1-8 parts by weight of the sulfur, arsenic and phosphorus purifying agent.
6. The sulfur, arsenic and phosphorus purifying agent as claimed in claim 1, wherein the content of manganese oxide is 1-4 parts by weight of the sulfur, arsenic and phosphorus purifying agent.
7. The sulfur, arsenic and phosphorus scavenger of claim 1, wherein the bulk density of the sulfur, arsenic and phosphorus scavenger is less than 1.0kg/m3The lateral pressure intensity is more than 70N/grain.
8. The sulfur, arsenic and phosphorus scavenger according to claim 1, wherein the lubricant is at least one of graphite, talc, sesbania powder and stearic acid.
9. The sulfur, arsenic and phosphorus scavenger as defined in any one of claims 1 to 8, which is used for purification of natural gas, synthesis gas and light gas liquid hydrocarbons.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978594A (en) * | 2005-12-09 | 2007-06-13 | 上海化工研究院 | Liquid-state petroleum hydrocarbon dearsenicing agent with dual medium-hole structure distribution and preparing method thereof |
| CN105214599A (en) * | 2014-07-03 | 2016-01-06 | 中国石油化工股份有限公司 | Sulphur arsenic adsorbent and preparation method thereof |
| CN105233806A (en) * | 2015-10-20 | 2016-01-13 | 昆明理工大学 | Preparation method of adsorbent for purifying hydrogen sulfide, hydrogen phosphide and arsenic hydride simultaneously |
| CN105582877A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Normal-temperature desulfurization dearsenic agent and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978594A (en) * | 2005-12-09 | 2007-06-13 | 上海化工研究院 | Liquid-state petroleum hydrocarbon dearsenicing agent with dual medium-hole structure distribution and preparing method thereof |
| CN105214599A (en) * | 2014-07-03 | 2016-01-06 | 中国石油化工股份有限公司 | Sulphur arsenic adsorbent and preparation method thereof |
| CN105582877A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Normal-temperature desulfurization dearsenic agent and preparation method thereof |
| CN105233806A (en) * | 2015-10-20 | 2016-01-13 | 昆明理工大学 | Preparation method of adsorbent for purifying hydrogen sulfide, hydrogen phosphide and arsenic hydride simultaneously |
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