WO2021063345A1 - 一种脱砷吸附剂及其制备方法 - Google Patents

一种脱砷吸附剂及其制备方法 Download PDF

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WO2021063345A1
WO2021063345A1 PCT/CN2020/118768 CN2020118768W WO2021063345A1 WO 2021063345 A1 WO2021063345 A1 WO 2021063345A1 CN 2020118768 W CN2020118768 W CN 2020118768W WO 2021063345 A1 WO2021063345 A1 WO 2021063345A1
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adsorbent
copper
arsenic
composition
zno
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PCT/CN2020/118768
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English (en)
French (fr)
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卓润生
张青
张平
王洪飞
刘新生
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四川润和催化新材料股份有限公司
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Priority to EP20870628.3A priority Critical patent/EP4023329A4/en
Publication of WO2021063345A1 publication Critical patent/WO2021063345A1/zh

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    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01J20/08—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 comprising aluminium oxide or hydroxide; comprising bauxite
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
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    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • B01D2257/60—Heavy metals or heavy metal compounds

Definitions

  • the invention relates to a dearsenic adsorbent, more specifically, the present invention relates to a copper-based dearsenic adsorbent for removing arsenic in low-carbon olefins such as propylene at room temperature, and belongs to the technical field of petrochemical industry.
  • Low-carbon olefins such as propylene are the basic organic raw materials in the petrochemical industry in large demand and wide-ranging applications. They are widely used in the production of chemical products such as polypropylene.
  • the supply of propylene mainly comes from the by-products of the process of naphtha cracking to ethylene and heavy oil catalytic cracking.
  • Petroleum contains many elements and their compounds that are harmful to the petroleum processing process, and arsenic is one of them.
  • arsenic content in oil products has shown an upward trend year by year.
  • Daqing oil and Xinjiang oil in my country's crude oil are both high-arsenic crude oils, especially Daqing oil has the highest arsenic content in the world.
  • Arsenic compounds are widely present in various petroleum hydrocarbons. Products obtained from secondary processing of high-arsenic oil products, such as propylene and ethylene, also contain arsenic compounds to varying degrees.
  • arsenic compounds The most prominent problem caused by arsenic compounds is the poisoning of catalysts. They have a permanent poisoning effect on many catalysts in petroleum hydrocarbon processing. Some deep-processing catalysts often require that the arsenic content must be very low, otherwise it will cause catalyst poisoning and lead to reactions. Unable to proceed. Therefore, the content of arsenic in petroleum hydrocarbons must be controlled within a certain standard, so as not to affect the activity and service life of the catalyst.
  • the propylene polymerization process in industrial production requires that the arsenic content in propylene should not be higher than 20ng/g, otherwise the polymerization reaction will not proceed normally and the degree of polymerization will decrease. Therefore, polymer grade propylene generally controls the arsenic content below 10ng/g, or even lower.
  • the arsenic content in propylene is directly related to the source of propylene.
  • the arsenic content in the raw materials of some domestic polypropylene manufacturers is as high as 200 ng/g or even 10,000 ng/g, and these manufacturers have encountered an urgent need to solve the problem of arsenic removal. Therefore, the removal of arsenic in petroleum hydrocarbons such as propylene is of great significance.
  • Most of the arsenide in propylene is arsine. Therefore, the problem of arsenic removal of propylene is actually the problem of arsine removal.
  • Oxidative arsenic removal use potassium permanganate and cumene hydrogen peroxide as oxidants to treat petroleum hydrocarbons, and then remove inorganic arsenic by water elution. This method is prone to produce arsenic-containing waste liquid, large wastewater treatment volume, and pollute internal components and surroundings.
  • Catalytic hydrodearsenic Dearsenic in the catalytic process of hydrorefining. This method is commonly used in reforming equipment, such as CN1030440A, CN1113261A, CN1136070A, CN201210556486.8, CN1030440A, CN1030440A, CN98100761.9, CN93105866.X , CN201310342825.7, CN98100762.7, CN201510920454.5 and other Chinese patents, and US2003/0111391A1 all involve the catalytic hydrogenation dearsenic process, but those skilled in the art know that the above process and/or dearsenic agent are all It is only suitable for the removal of arsenic from liquid hydrocarbons under high temperature and hydrogen conditions. It needs to operate under high temperature and high pressure conditions. The operation process is complicated, the operation cost is high, and it is easy to coke, which leads to a shortened service cycle.
  • Adsorption removal of arsenic such as the use of silicon-aluminum pellets and copper-sulfate-loaded silicon-aluminum pellets to remove trace arsenic in liquid petroleum hydrocarbons.
  • the process of adsorbing arsenic is simple, but it is difficult to remove high-boiling arsenic compounds, the depth of arsenic removal is not high, the adsorption capacity of the adsorbent for arsenic is small, and the service life is short.
  • the adsorption process of arsenic removal has attracted attention because of its simplicity, ease of handling, and high efficiency. As disclosed and described in documents such as US Pat. Nos. 4,593,148, USP 5064626, USP 5085844, USP 5,096,681, USP 5,096,682.
  • USP53782076 discloses a lead-based dearsenic agent made of alumina as a carrier and a certain amount of lead oxide. , It is suitable for the dearsenication of materials containing gaseous hydrocarbons, but when the materials contain impurities such as sulfides, such as hydrogen sulfide, the dearsenication efficiency will be greatly reduced.
  • US4849577 and CN200810113631.9 disclose lead-based dearsenic agents that can simultaneously remove arsenic and carbon, oxygen, and sulfur compounds in liquid hydrocarbons.
  • the carrier is alumina and the active component is lead oxide, but it is still not applicable For the removal of arsenic from gaseous hydrocarbons with higher sulfur content.
  • Lead-based dearsenic agents generally have the defect of low dearsenic adsorption capacity.
  • CN200810114094.X, CN200810113359.4, CN200810114092.0, and US Patent US5990372 disclose that alumina and clay are used as carriers, iron oxide is used as the active center, but oxides such as lead are still used as auxiliary agents for desorption.
  • Arsenic has a high sulfur capacity, but its capacity to adsorb arsenic is still low.
  • Copper-based dearsenic agents are silica-alumina pellets or activated carbon impregnated with 5%-10% copper sulfate.
  • the catalytic activity of the copper sulfate-silica-alumina pellet adsorption method is low, and the arsenic capacity is small, only 0.1% to 0.3% ,
  • the operation cycle is also short, the consumption is large, a large amount of waste catalyst is difficult to deal with in time, and it is easy to cause environmental pollution.
  • the copper-zinc dearsenic agent prepared by Chinese patents CN1093526C and CN200810113132.X using alumina etc. as a carrier is suitable for the removal of arsenic from gaseous materials.
  • Chinese patent CN1197052A discloses a kind of dearsenic agent containing at least one kind of copper oxide or copper sulfide deposited on alumina ball and silica carrier. It is completely free in a wide temperature range and under low pressure. Under the condition of hydrogen, arsenic is removed from the liquid hydrocarbon feedstock.
  • Chinese patent CN1278523A also discloses a catalyst for removing trace arsenide from hydrocarbons at room temperature and a preparation method thereof. It is composed of CuO, ZnO, and Al 2 O 3. It also specifically mentions the composition containing noble metals for modification, but noble metals will improve its cost. In addition, CN1580196A also improves the performance of removing high-boiling arsenic from liquid petroleum hydrocarbons at low or normal temperature by improving the arsenic removal agent.
  • Chinese patent CN103316690A proposes a method that uses CuO as the active component, transition metal La 2 O 3 , CeO 2 and noble metal Pd, Ag oxides as additives, activated carbon as the carrier, and is prepared by one carrier pretreatment and three impregnation. Into the dearsenic agent. Activated carbon as a carrier can increase the pore volume of the adsorbent.
  • Chinese patent CN200510110226.8 mentions the arsenic removal adsorbent prepared by the combination of active carbon and iron oxide, which has the characteristics of high capacity, high selectivity and high adsorption rate, and can remove water or Arsenic in atmospheric smoke.
  • Chinese Patent CN102553517B discloses a waste catalyst powder obtained by burning carbon, grinding, and sieving waste silicon-aluminum catalyst, and adding an extruding aid together with alumina to dry-mix the catalyst powder.
  • the nitric acid solution and deionized water are mixed and kneaded to form the extruded bar, dried and calcined to obtain a carrier, and the active component copper and zinc oxides are loaded on the carrier, and then dried and calcined to obtain a light oil adsorption dearsenic agent.
  • Chinese patent CN1043151C discloses a method for preparing a dearsenic agent with dual pore distribution and also used for petroleum distillate oil containing arsenic liquid hydrocarbons.
  • the arsenic removal agent has a wide pore size distribution and a small specific surface area. It can be used for the arsenic removal reaction of arsenic-containing liquid hydrocarbons at 80-250 °C after reduction, passivation, activation and other treatment steps before use.
  • the catalyst is not suitable for arsenic removal at room temperature.
  • Chinese patent CN1667091A discloses a composite oxide formed by one or two of mesoporous molecular sieves, double-pored molecular sieves, silicon dioxide, aluminum oxide, magnesium oxide, zinc oxide, and silicon aluminum oxide as a support
  • the oxide carrier of the active component is composed of the V or VI main group compound of the five elements of copper, iron, manganese, silver, and palladium, or two of its zero-valent metals as the active component for removing arsenic. Synthetic room temperature dearsenic agent.
  • Chinese patents CN200610117961.6, CN200510111322.4, and CN 200510029344.6 also disclose the use of a molecular sieve with a double mesoporous-microporous structure as a carrier material and an active metal copper, iron, manganese, nickel, silver and other dearsenic agents.
  • This kind of dearsenic agent not only has dearsenic performance, but also has better water resistance.
  • Chinese patent CN 103566947 A discloses a room temperature dearsenic agent and a preparation method thereof. It uses manganese dioxide, copper oxide, and zinc oxide as active components, and adds one of binders, pore formers, and extrusion aids. A variety of copper-based dearsenic agents synthesized as auxiliary agents. The introduction of pore formers has certain advantages in increasing the proportion of macropores of the adsorbent, but the improvement of pore volume is very limited.
  • Arsenic compounds in petroleum hydrocarbons are mainly trivalent organic complexes, and organic arsenic compounds with different boiling points will enter various fractions of crude oil after fractionation.
  • liquid petroleum hydrocarbons also contain a considerable amount of high-boiling arsenic compounds such as As(CH 3 ) 3 , AS (C 2 H 5 ) 3 and so on.
  • As(CH 3 ) 3 the higher the boiling point of the arsenide or the longer the chain length of the hydrocarbon group, the less easily it can be removed and the higher the requirement for the dearsenic agent.
  • the removal effect of high-boiling arsenic compounds with copper compounds as active components is not ideal, and the arsenic capacity of the arsenic removal agent is less than 0.1%.
  • the existing technology generally has low arsenic capacity and poor dearsenic efficiency; it is easily disturbed during use and has a short service cycle. ;
  • the adsorbent has a small porosity and poor water resistance; a large amount of active metal used and a low effective utilization rate; a large heap ratio, high cost of one-time filling, high cost, and so on.
  • the arsenic removal agents are mostly composed of carriers and active components.
  • the carriers include molecular sieves, alumina, silica, etc.; the active components are mostly copper, iron, manganese, and silver. , Palladium, nickel and other transition metal compounds.
  • the preparation of the dearsenic agent mainly uses the conventional dipping method, co-precipitation method, decomposition method, mechanical mixing method and other methods.
  • the uniform and effective dispersion of the active components on the carrier also needs to reach a certain optimal state.
  • the arsenic removal agent for light hydrocarbon materials such as propylene and ethylene
  • a high activity, large adsorption capacity, high arsenic removal accuracy and selectivity have been developed for this purpose, and it is used in industrial processes.
  • Arsenic removal adsorbent with good mechanical strength and water resistance. It is very meaningful.
  • the purpose of the present invention is to overcome the above-mentioned defects in the prior art, and to provide a high arsenic adsorption capacity, good adsorption selectivity, excellent arsenic removal performance, good water resistance and mechanical strength during industrial use.
  • the purpose of the present invention is achieved through the following technical routes and implementations. Due to the rapid development of high pore volume porous adsorption material preparation technology, it has adjustable pore size distribution, stable carrier structure, large and modifiable inner surface of pores, It will bring certain advantages in the adsorption process. When it is used as an adsorbent or a catalyst carrier, it can exert the maximum adsorption reaction efficiency together with the active components.
  • the pore volume of the agent is 0.1 to 0.9 ml/g, and the preferred pore volume is 0.3 to 0.7 ml/g.
  • the precursor composition of macroporous ⁇ -Al 2 O 3 and nano-ZnO is uniformly mixed by one selected from the group consisting of dry method, wet method, and liquid phase mixing method, and is uniformly mixed by rolling balls, oil column forming, and extrusion.
  • One of the strip-cutting-shaping method which prepares the mixture into small balls;
  • Adopt one of the stepwise and mixed impregnation methods impregnate the acidified solution of the copper compound and the rare earth composition, and dry at 100-250°C for 0.5-15 hours.
  • the impregnation and drying steps can be alternately repeated 1 to 5 times; preferably The dipping and drying steps are repeated alternately 1 to 2 times.
  • the dried material is fired and activated at 300-650°C for 0.5-15 hours; the preferred firing activation conditions are firing and activation at 350-500°C for 1 to 5 hours.
  • n in the preferred Al 2 (OH) n Cl 6- n is 4.0 ⁇ 4.8.
  • the arsenic removal adsorbent provided by the present invention is characterized in that the precursor of the macroporous ⁇ -Al 2 O 3 is aluminum hydroxide xerogel powder prepared by the aluminum sulfate method, and the macroporous ⁇ -Al 2 O 3 is formed after roasting.
  • -Al 2 O 3 has a pore volume of 0.4 to 1.2 ml/g, preferably 0.6 to 0.9 ml/g; macroporous ⁇ -Al 2 O 3 is a hydroxide prepared by the macroporous alumina powder precursor and aluminum sulfate method Aluminum xerogel powder, in the preparation process of the present invention, ⁇ -Al 2 O 3 with high pore volume is formed after calcination, which is easy for the diffusion of hydrocarbon molecules; the aluminum hydroxide xerogel powder prepared by the aluminum sulfate method can easily pass the commercial Purchased.
  • the adsorbent for removing arsenic provided by the present invention is characterized in that the nano-ZnO precursor is basic zinc carbonate.
  • the nano-ZnO formed and the precursor decomposition process make the composite carrier have high The pore volume and the easy channel for the diffusion of hydrocarbon molecules; basic zinc carbonate can be easily obtained commercially.
  • the arsenic removal adsorbent provided by the present invention is characterized in that the copper compound is one of copper tartrate, copper oxide, copper hydroxide, copper carbonate, copper sulfate, copper nitrate, copper acetate, and copper chloride Or more; preferred is copper nitrate; these copper compounds can be conveniently obtained commercially.
  • the adsorbent for removing arsenic provided by the present invention is characterized in that the rare earth composition is a compound of lanthanum and cerium or a mixture rich in lanthanum and cerium; in the present invention, these rare earth compositions are used as active component additives For use, it can be easily obtained commercially.
  • the arsenic removal adsorbent provided by the present invention is characterized in that the acidified solution is a solution obtained after acidification with nitric acid; the degree of acidification has a direct effect on the strength of the structure of the adsorbent, and nitric acid can be conveniently obtained commercially.
  • the arsenic-removing adsorbent provided by the present invention is applied to the industrial propylene dearsenic-removal adsorption purification process, which can be used at normal temperature and lower temperature ( ⁇ 100°C), normal pressure and space velocity of 1200-2100 hours -1 , Or it can be used under the condition that the liquid space velocity is 4.5 to 8.0 hours -1.
  • the dearsenic adsorbent provided by the present invention has a high pore volume and a larger internal surface area of the carrier pores, and can better disperse the active components, thereby increasing the active composition of the dearsenic agent.
  • the effective contact area with the arsenide allows the active components to exert the adsorption reaction efficiency.
  • the composite carrier can provide a larger large-pore diameter diffusion channel, which is conducive to improving the diffusion and transmission performance of arsenic-containing petroleum hydrocarbon media. It has good adaptability to the complex components in petroleum hydrocarbons, and can operate at room temperature and lower temperature. Improve the efficiency of arsenic removal under conditions, quickly remove arsenic in liquid petroleum hydrocarbons, and can adapt to changing working conditions.
  • the raw material hydrocarbon contains a small amount of impurities such as sulfide and water, it will greatly interfere with the adsorption and purification process.
  • the arsenic removal adsorbent of the present invention has high competition. Adsorption selectivity can still maintain and achieve good arsenic removal accuracy and effect.
  • the dearsenic adsorbent of the present invention has better mechanical strength than the prior art purification adsorbent when used under such working conditions with high impurity content, thereby prolonging the stable operation period.
  • the arsenic-removing adsorbent of the present invention is under normal or lower temperature conditions and non-hydrogen use conditions, so that the operation process is simpler and safer, the arsenic removal process is simplified, the cost of arsenic removal is reduced, and The arsenic-removing adsorbent will not produce arsenic-containing waste liquid and pollute the environment during industrial use.
  • the BET low-temperature nitrogen adsorption method is used to determine the pore capacity of the sample; the mechanical strength performance of the adsorbent sample is tested with reference to the catalyst abrasion and crushing strength determination method.
  • Other tests can refer to ("Petroleum and Petroleum Products Test Methods National Standards” published by China Standard Press in 1989) and ("Petrochemical Analysis Methods (RIPP Test Methods)” published by Science Press in 1990).
  • the commercially available spherical ⁇ -Al 2 O 3 (industrial product, Shandong Zibo Jiarun Chemical Co., Ltd., alumina ⁇ 99.9wt%) was impregnated with copper nitrate (same as above) solution, and the CuO content was the same as in Example 1, and dried After calcination and activation, the calcination activation conditions are the same as in Example 1, and the copper-alumina type dearsenic adsorbent is prepared.
  • copper nitrate (same as above), zinc nitrate (industrial product, Shijiazhuang Xuanran Chemical Product Sales Co., Ltd., Zn(NO 3 ) 2 6H 2 O ⁇ 98wt%), aluminum nitrate (Industrial product, Shanghai Jiupeng Chemical Co., Ltd., aluminum nitrate ⁇ 98.5wt%), and the CuO and ZnO content are the same as in Example 1. After drying, they are molded and fired to activate. The firing and activation conditions are the same as in Example 1, to prepare copper -Zinc-alumina type dearsenic adsorbent.
  • the shaped material After the shaped material is dried in an industrial oven at 110°C for 6 hours, it is immersed A mixed solution of 6500 grams of copper nitrate (same as above), 1000 grams of cerium nitrate (same as above), 200 grams of nitric acid (same as above) and deionized water, dried in an industrial oven at 110°C for 4 hours, and then placed in an industrial muffle furnace at 380°C After calcination and activation for 4 hours, the adsorbent for removing arsenic in Example 2 was prepared.
  • the shaped material After the shaped material is dried in an industrial oven at 120°C for 3 hours, it is divided The mixed solution of 5000 grams of copper nitrate (same as above), 400 grams of cerium-rich rare earth chloride (same as above), 200 grams of nitric acid (same as above) and deionized water is impregnated on the composite carrier by the method of multiple dipping and drying.
  • the drying conditions are It was dried at 120°C for 2 hours, and then calcined and activated in an industrial muffle furnace at 330°C for 10 hours to prepare the arsenic removal adsorbent of Example 3.
  • the arsenic removal adsorbents of Examples 1 to 3 and Comparative Examples 1 to 2 were tested for adsorption and arsenic removal performance on a micro-evaluation device.
  • the test conditions are normal temperature, normal pressure, space velocity of 1600 ⁇ 1800 hours -1 , and the loading capacity of arsenic removal agent is 20 ml.
  • the raw material is industrial propylene raw material of a chemical plant with purity > ⁇ 99.5% and arsenic content of 1600 ⁇ 1800ng/g, sulfur content ⁇ 18mg/m 3 , water content ⁇ 50 ⁇ g/g.
  • the outlet arsenic content is greater than 10ng/g, the adsorption reaction process is stopped, as a test operation cycle, the results of the test are listed in Table 1 below.

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Abstract

一种脱砷吸附剂及其制备方法，其特征是以占吸附剂总量计的组成中含有：10～40wt％的CuO、5～30wt％的ZnO、1～20wt％的CaO、0.1～10wt％的Cl -、0.1～10wt％的稀土氧化物和余量的Al2O3，复合载体由大孔γ-Al2O3、纳米ZnO组合物形成的高孔容内核，和CaCl2、Al2(OH)nCl6-n组合物涂覆形成的外层所共同构成，其中n为1～5；复合载体浸渍铜化合物、稀土组合物的酸化溶液后干燥、焙烧活化；得到的脱砷吸附剂的孔容为0.1～0.9毫升/克；应用于丙烯的脱砷吸附的实际工业净化过程中时，具有脱砷精度和吸附选择性高，吸附砷容量大，耐硫、耐水性能和机械强度好的特点。

Description

一种脱砷吸附剂及其制备方法 技术领域
本发明涉及一种脱砷吸附剂，更具体地说，本发明涉及一种常温除去丙烯等低碳烯烃中砷化物的铜系脱砷吸附剂，属于石油化工技术领域。
背景技术
丙烯等低碳烯烃是石油化学工业中需求量大和用途很广的基本有机原料，广泛用于生产聚丙烯等化工产品；丙烯供应主要来自石脑油裂解制乙烯和重油催化裂解过程的副产品。
石油中含有许多对石油加工过程有害的元素及其化合物，砷化物就是其中之一。近些年来，随着原油开采的不断进行，油品中砷含量呈逐年上升的趋势。我国原油中大庆油和新疆油均属高砷原油，尤其是大庆油砷含量被认为是世界最高的。砷化物广泛存在于各类石油烃中，高砷油品二次加工所得的产品，如丙烯、乙烯等物料也不同程度含有砷化物。
这些石油烃特别是液态石油烃中的砷化物会对其后续加工有着明显的负面影响。砷化物除容易沉积在管道表面，腐蚀管道，造成隐患，严重时，砷化物将会使某些工艺过程不能顺利进行。
砷化物所引起的最突出的问题还是造成催化剂的中毒，它们对石油烃加工中的许多催化剂具有永久性的中毒作用，一些深加工催化剂往往要求砷含量必须很低，否则会引起的催化剂中毒导致反应无法进行。因此石油烃中的砷化物含量必须控制在一定的标准之内，以免影响催化剂的活性和使用寿命。
在烯烃工业中，烃类裂解、催化重整、加氢工艺，特别是聚合工艺过程中，原料中极少量的砷化物就可能使催化剂中毒而降低催化活性，严重影响产品的质量和经济效益。例如，乙烯装置中使原料中的砷化物尽可能地降低是非常必要的，为了保护下游贵金属加氢催化剂免受砷中毒而降低催化活性，一些装置中设置了裂解产物的后脱砷工艺，要求将C 2、C 3及其混合物料中的砷脱除。
工业生产中的丙烯聚合工艺，则要求丙烯中的砷含量不能高于20ng/g，否则会导致聚合反应不能正常进行，聚合度降低。因此聚合级丙烯一般控制砷含量在l0ng/g以下，甚至更低。
丙烯中的砷含量高低与丙烯的来源直接相关。目前，国内有的聚丙烯厂家原料中砷含量高达200ng/g甚至10000ng/g，这些厂家都遇到了迫切需要解决 的脱砷问题。因此，脱除丙烯等石油烃中的砷化物具有十分重要的意义。丙烯中的砷化物绝大多数的存在状态为砷化氢，因此，丙烯的脱砷问题实际上就是砷化氢的脱除问题。
为了脱除石油烃中的砷，人们进行了长期的研究，提出了各种各样的脱砷方法和制备了各种各样的脱砷剂，目前常用的液态烃脱砷方法主要有以下三种：
氧化脱砷：以高锰酸钾和过氧化氢异丙苯等为氧化剂处理石油烃，再经水洗脱除无机砷化物，该方法易产生含砷废液、废水处理量大、污染内部构件和环境。
催化加氢脱砷：加氢精制催化过程脱砷，此方法在重整等装置上是较为常用的方法，在CN1030440A、CN1113261A、CN1136070A、CN201210556486.8、CN1030440A、CN1030440A、CN98100761.9、CN93105866.X、CN201310342825.7、CN98100762.7、CN201510920454.5等中国专利，以及US2003/0111391A1中都涉及到了催化加氢脱砷过程，但熟悉本领域的技术人员均知晓，上述过程和/或脱砷剂都只适应于高温、临氢条件下的液态烃脱砷，需在高温、高压的条件下运行，操作过程复杂，运行成本高，且易结焦，导致使用周期缩短。
吸附脱砷：如采用硅铝小球及负载硫酸铜的硅铝小球脱除液态石油烃中的微量砷化物。对于大多数应用场合来说，吸附脱砷的工艺简单，但难脱除高沸点砷化物，脱砷深度不高，吸附剂对砷的吸附容量小，使用寿命短。在工业上所使用的预脱砷三种主要方法中，吸附方法脱砷过程以其简便、易处理、效率高等特点受到关注。如在美国专利US4593148、USP5064626、USP5085844、USP5096681、USP5096682等文献中所公开和描述的那样。
现有技术中使用较多的脱砷剂有铅系和铜系脱砷剂，如USP53782076中就公开了一种以氧化铝为载体，担载一定量的氧化铅制成的铅系脱砷剂，适用于包含气态碳氢化合物的物料的脱砷，但当物料中含有硫化物等杂质时，比如硫化氢，脱砷效率就会大大降低。现有技术中US4849577、CN200810113631.9公开了能够同时脱除液态烃中的砷和碳氧硫化合物的铅系脱砷剂，其中的载体是氧化铝、活性组分为氧化铅，但仍不适用于硫含量较高的气态烃的脱砷。铅系脱砷剂普遍存在脱砷吸附容量较低的缺陷。
现有技术中CN 200810114094.X、CN200810113359.4、CN 200810114092.0，以及美国专利US5990372公开了以氧化铝及粘土为载体，以氧化铁为活性中心，但仍要以铅等氧化物为助剂的脱砷剂，具有高的硫容，但吸附砷的容量仍较低。
常用的铜系脱砷剂是浸渍有5％～10％硫酸铜的硅铝小球或活性炭，硫酸铜硅铝小球吸附法的催化剂活性低，容砷量小，仅为0.1％～0.3％，运转周期也较短，消耗量较大，大量的废催化剂难以及时处理，容易造成环境污染。
与本发明一样采用铜氧化物为主要活性组元的铜系脱砷剂的现有技术专利有许多，如中国专利CN1197052A公开了一种从液体烃原料中除去砷的方法，该方法使用的脱砷剂为沉积在载体上的铜的氧化物或铜的硫化物，且该方法在没有氢存在的低温、低压条件下运行。其制备涉及到复杂的硫化过程，因此脱砷活性组份至少部分以铜的硫化物存在。
中国专利CN1093526C、CN200810113132.X以氧化铝等为载体，所制备出的铜-锌脱砷剂，适合于气态物料中的砷脱除。中国专利CN1197052A公开了一种含有至少一种沉积在氧化铝球、氧化硅载体上的铜的氧化物或铜的硫化物作为脱砷剂，在很宽的温度范围内，以及低压下，完全没有氢气的条件下，从液体烃原料中除去砷。
中国专利CN1278523A也公开了一种常温脱除烃中微量砷化物的催化剂及其制备方法，其由CuO、ZnO、A1 2O 3，还特别提到了含有贵金属组成进行改性，但贵金属会提高其成本。此外，CN1580196A还通过改进提高了在低温或常温脱除液态石油烃中高沸点砷化物性能的脱砷剂。
中国专利CN103316690A提出了一种由CuO为活性组分，由过渡金属La 2O 3、CeO 2和贵金属Pd、Ag的氧化物为助剂、活性炭为载体，通过一次载体预处理和三次浸渍制备而成的脱砷剂。活性炭为载体能够提高吸附剂的孔容，如中国专利CN200510110226.8提到了由活性炭与氧化铁复合制备的除砷吸附剂，具有高容量、高选择性和高吸附率等特性，可去除水中或大气烟气中的砷。
采用其他一些多孔材料进行改性也有报道，如中国专利CN102553517B公开了一种将废硅铝催化剂，经烧碳、研磨、筛分得到废催化剂粉末，和氧化铝一起加入助挤剂干混，并加入硝酸溶液和去离子水混捏挤条成型，经干燥、焙烧得到载体，并将活性组分铜和锌的氧化物负载于载体上，再经干燥、焙烧得到轻油吸附脱砷剂。中国专利CN1043151C则公开了一种具有双孔分布的也是用于石油馏分油含砷液态烃的脱砷剂的制备方法。该脱砷剂具有较宽的孔径分布和较小的比表面积，在使用前经还原、钝化、活化等处理步骤后在80～250℃下用于含砷液态烃的脱砷反应，但该催化剂不适用于常温脱砷。
中国专利CN1667091A公开了一种由中孔分子筛、双孔分子筛、二氧化硅、三氧化二铝、氧化镁、氧化锌、硅铝氧化物中的一种或者两种形成的复合氧化 物作为支载活性组分的氧化物载体，由铜、铁、锰、银、钯五种元素的第V或VI主族化合物，或其零价态金属中的两种复合而成作为脱砷活性组分，合成常温脱砷剂。
中国专利CN200610117961.6、CN200510111322.4、CN 200510029344.6也公开了使用双中孔-微孔结构的分子筛为载体材料，并配以活性金属铜、铁、锰、镍、银等的脱砷剂，这种脱砷剂在具有脱砷性能的同时，还具有较好的耐水性能。
中国专利CN 103566947 A公开了一种常温脱砷剂及其制备方法，以二氧化锰、氧化铜、氧化锌为活性组分，加入粘结剂、造孔剂、助挤剂中的一种或多种为助剂而合成的一种铜系脱砷剂，造孔剂的引入对提高吸附剂的大孔比例有一定的好处，但对孔容的提高十分有限。
石油烃中的砷化物主要为三价有机配合物，具有不同沸点的有机砷化合物将分别进入到原油分馏后的各种馏份当中。液态石油烃除了含有一定量的低沸点砷化物如AsH 3外，还含有相当量的高沸点砷化物如As(CH 3) 3、A S(C 2H 5) 3等。砷化物沸点越高或烃基链长越长，其越不容易被脱除，对脱砷剂要求也越高。从专利文献提供的技术数据来分析，以铜化合物为活性组份对高沸点砷化物的脱除效果并不理想，脱砷剂的砷容量不足0.1％。
由于液态石油烃吸附脱砷过程的影响因素十分复杂，因此对脱砷剂的要求也较高，现有技术中普遍存在砷容量低、脱砷效率差；使用过程中易受干扰，使用周期短；吸附剂孔隙率小、耐水性能差；活性金属使用量大、有效利用率低；堆比重大，一次装填费用偏高、成本高等等问题。
发明内容
从上述现有技术中可以看出，脱砷剂多由载体和活性组分构成，其中，载体大多包括分子筛类、氧化铝、二氧化硅等；活性组分多选用铜、铁、锰、银、钯、镍等过渡金属元素的化合物。
脱砷剂的制备主要使用常规的浸渍法、共沉淀法、分解法、机械混合法等方法，活性组分在载体上的均匀和有效分散也需要达到一定的最佳状态。由于丙烯、乙烯等轻烃物料的脱砷剂在石油化工生产中有着十分重要的应用，为此开发一种活性高、吸附砷容量大、脱砷精度和选择性较高，且在工业使用过程中有较好机械强度和耐水性能的脱砷吸附剂。是十分有意义的。
本发明的目的就是为了克服上述现有技术中存在的缺陷，而提供一种在工 业使用过程中具有砷吸附容量高、吸附选择性好、脱砷性能优良且耐水性能和机械强度好的，具有高孔容、易扩散和带有保护层核-壳结构的液态石油烃常温脱砷剂及其制备方法。
本发明的目的是通过以下技术路线和实施方案来实现的，由于高孔容多孔吸附材料制备技术得到了快速的发展，具有可调孔径分布、稳定的载体结构、较大且可修饰的孔道内表面，在吸附过程中会带来一定的优越性，被用作吸附剂或催化剂载体时，能和活性组元一起发挥最大的吸附反应效能。
这些新型多孔材料制备技术用于制备低碳烯烃脱砷吸附剂时，一方面能提供较大的孔道内表面积，引入活性组分后将能较好地分散活性组分，另一方面又能提供较大的大孔径扩散通道，有利于改善含砷石油烃介质的传输性能，再以合适的方式将吸水性能好的组分植入到核-壳结构的外层结构中形成保护层，就有可能得到适合于常温、低温下具有高脱砷性能的净化吸附剂。
本领域技术人员均熟知，孔道容量、孔隙率和结构分布是影响吸附材料吸附反应过程、吸附容量、选择性和净化精度等性能的重要因素，且与吸附剂机械使用强度和反应性能之间存在着十分复杂的非线性关联关系，有关这些内容可以通过阅读参考(“Heterogeneous Catalysis In Practice”Charles N.Satterfield,p334-344(1980,McGraw-Hill))等书籍和文献，来了解孔道的吸附扩散及和使用强度、机械性能等方面的知识。
但就目前的催化理论和技术水平而言，还不能做到准确的理论推导或经验预测；也不能通过简单的条件试验和排列组合试验，在孔道体系和吸附性能、反应性能、使用机械强度间建立清晰的关联；对其调变和构成的制备技术往往还需要依靠经验积累，并构成了吸附剂制造技术方面的技术knowhow。在本发明中所运用的这些知识和经验同样构成了本发明吸附剂及其制备方法方面的技术knowhow。
本发明所提供的一种脱砷吸附剂，其特征是以占吸附剂总量计的组成中含有：10～40wt％的CuO、5～30wt％的ZnO、1～20wt％的CaO、0.1～10wt％的Cl -、0.1～10wt％的稀土氧化物和余量的Al 2O 3，复合载体由大孔γ-Al 2O 3、纳米ZnO组合物形成的高孔容内核，和CaCl 2、Al 2(OH) nCl 6-n(n＝1～5)组合物涂覆形成的外层所共同构成；复合载体浸渍铜化合物、稀土组合物的酸化溶液后干燥、焙烧活化；得到的脱砷吸附剂的孔容为0.1～0.9毫升/克，优选的孔容为0.3～0.7毫升/克。
本发明所提供的一种脱砷吸附剂的制备方法，一种脱砷吸附剂的制备方法， 其特征为制备过程包括如下步骤：
(1)将大孔γ-Al 2O 3、纳米ZnO的前驱体组合物采用选自干法、湿法、液相混合法中的一种混合均匀，并选用滚球、油柱成型、挤条-切粒-整型方式中的一种，将混合物料制备成小球型；
(2)将成型后的物料在100～250℃下干燥0.5～15小时，制备成复合载体的内核；
(3)将小球型内核在滚球机内将CaCl 2、Al 2(OH) nCl 6-n组合物涂覆在外层上构成复合载体，其中，n为1～5；
(4)采用分步、混合浸渍方法中的一种，浸渍铜化合物和稀土组合物的酸化溶液，100～250℃下干燥0.5～15小时，浸渍、干燥步骤可交替重复1～5次；优选的浸渍、干燥步骤交替重复1～2次。
(5)干燥后的物料经300～650℃下焙烧活化0.5～15小时；优选的焙烧活化条件为350～500℃下焙烧活化1～5小时。
这些制备过程和步骤中涉及到的混合、成型、涂覆、浸渍、干燥和焙烧方法为本领域技术人员所熟知和日常试验运用；制备过程中为了便于操作所添加的去离子水量可不受限制，在干燥和焙烧过程中绝大部分被挥发掉；涉及到的CaCl 2和Al 2(OH) nCl 6-n可以方便地通过商购获得，Al 2(OH) nCl 6-n在工业上也被称为铝溶胶，其组成与粘结性能有很大关系，对吸附剂的机械强度有较大影响，本发明中优选的Al 2(OH) nCl 6-n中的n为4.0～4.8。
本发明所提供的一种脱砷吸附剂，其特征在于所述的大孔γ-Al 2O 3的前驱体为硫酸铝法制备的氢氧化铝干凝胶粉，焙烧后形成的大孔γ-Al 2O 3孔容为0.4～1.2毫升/克，优选的是0.6～0.9毫升/克；大孔γ-Al 2O 3是通过大孔氧化铝粉前驱体，硫酸铝法制备的氢氧化铝干凝胶粉，在本发明的制备过程中，焙烧后形成的具有高孔容的γ-Al 2O 3，易于烃分子扩散；硫酸铝法制备的氢氧化铝干凝胶粉可以方便地通过商购获得。
本发明所提供的一种脱砷吸附剂，其特征在于所述的纳米ZnO前驱体是碱式碳酸锌，在本分明的制备过程中，形成的纳米ZnO，前驱体分解过程使复合载体具有高的孔容和易于烃分子扩散的通道；碱式碳酸锌可以方便地通过商购获得。
本发明所提供的一种脱砷吸附剂，其特征在于所述的铜化合物是酒石酸铜、氧化铜、氢氧化铜、碳酸铜、硫酸铜、硝酸铜、醋酸铜、氯化铜中的一种或多种；优选的是硝酸铜；这些铜化合物可以方便地通过商购获得。
本发明所提供的一种脱砷吸附剂，其特征在于所述的稀土组合物是镧、铈的化合物或富镧、富铈的混合物；在本发明中这些稀土组合物作为活性组元助剂使用，可以方便地通过商购获得。
本发明所提供的一种脱砷吸附剂，其特征在于所述的酸化溶液是经硝酸酸化后得到的溶液；酸化程度对吸附剂结构使用强度有直接影响，硝酸可以方便地通过商购获得。
本发明所提供的一种脱砷吸附剂应用于工业上丙烯的脱砷吸附净化过程，可在常温和较低温度(<100℃)下，常压、空速为1200～2100小时 -1，或者相当于液空速为4.5～8.0小时 -1的条件下使用。
与现有脱砷剂及其制备技术相比较，本发明所提供的脱砷吸附剂具有高孔容和较大的载体孔道内表面积，能较好地分散活性组分，从而提高了脱砷剂活性组分与砷化物的有效接触面积，使活性组分发挥吸附反应效能。
另一方面，复合载体又能提供较大的大孔径扩散通道，有利于改善含砷石油烃介质的扩散传输性能，对石油烃中的复杂成份具有良好的适应性，能够在常温、较低温度条件下提高脱砷效能，快速除去液态石油烃中的砷化物，并能适应变化较大的工况条件。
工业过程的原料中很难避免杂质的存在，当原料烃中含有少量硫化物和水等杂质的时候，会对吸附净化过程产生很大干扰，本发明的脱砷吸附剂由于具有很高的竞争吸附选择性，仍然能够维持和达到很好的脱砷精度和效果。同时，本发明的脱砷吸附剂在这种杂质含量较高的工况下使用时，具备优于现有技术净化吸附剂的机械使用强度，从而延长了稳定操作周期。
本发明的脱砷吸附剂由于在常温或较低温度条件下，和非临氢的使用条件，使操作过程更简便、安全性更好，简化了脱砷工艺，降低了脱砷的成本，并且脱砷吸附剂在工业使用过程中不会产生含砷废液而污染环境。
具体实施方式
在各实施例中，采用BET低温氮吸附法测定样品的孔容量；参照催化剂磨耗和压碎强度测定方法，测试吸附剂样品的机械强度性能。其它检测可以参照(《石油和石油产品试验方法国家标准》中国标准出版社出版1989年)和(《石油化工分析方法(RIPP试验方法)》科学出版社出版1990年)中的相关分析方法。
实施例1
将7800克氢氧化铝干胶粉(工业品，山东星都石油化工科技股份有限公司，氢氧化铝≮68wt％)，和3500克碱式碳酸锌粉(工业品，杭州龙卷风化工有限公司，锌≮57wt％)，经湿法混合均匀，经小型捏合机捏合后，在小型转盘滚球机上滚制成Φ5毫米的球形，再在滚球机上涂敷2500克铝溶胶(工业品，四川润和催化新材料股份公司，氧化铝≮20wt％)与1100克氯化钙粉(工业品，潍坊创辉化工有限公司，氯化钙≮74wt％)以及去离子水的混合物料，成型后的物料在工业烘箱中120℃干燥4小时后，浸渍6000克硝酸铜(工业品，济南源茂化工有限公司，98wt％)、250克氯化镧(工业品，乐山盛和稀土股份有限公司，TREO≮45wt％)、150克硝酸(工业品，南京润桥精细化工有限公司，≮68wt％)和去离子水的混合溶液，工业烘箱中120℃下干燥2小时后，再在工业马弗炉中350℃下高温焙烧6小时，制备成实施例1的脱砷吸附剂。
比较例1
在市售商品球形γ-Al 2O 3(工业品，山东淄博佳润化工有限公司，氧化铝≮99.9wt％)上浸渍硝酸铜(同上)溶液，并使CuO含量与实施例1相同，干燥后焙烧活化，焙烧活化条件与实施例1相同，制备成铜-氧化铝型脱砷吸附剂。
比较例2
按现有技术中所公布的共沉淀法，以硝酸铜(同上)、硝酸锌(工业品，石家庄轩然化工产品销售有限公司，Zn(NO 3) 2 6H 2O≮98wt％)、硝酸铝(工业品，上海九鹏化工有限公司，硝酸铝≮98.5wt％)，并使CuO、ZnO含量与实施例1相同，干燥后成型并焙烧活化，焙烧活化条件与实施例1相同，制备成铜-锌-氧化铝型脱砷吸附剂。
实施例2
将7600克氢氧化铝干胶粉(同上)，和2800克碱式碳酸锌粉(同上)，经湿法混合均匀，经小型捏合机捏合后，挤条、切粒并整型成Φ5毫米的球形， 再在滚球机上涂敷3000克铝溶胶(同上)与1400克氯化钙粉(同上)以及去离子水的混合物料，成型后的物料在工业烘箱中110℃干燥6小时后，浸渍6500克硝酸铜(同上)、1000克硝酸铈(同上)、200克硝酸(同上)和去离子水的混合溶液，工业烘箱中110℃下干燥4小时后，再在工业马弗炉中380℃下焙烧活化4小时，制备成实施例2的脱砷吸附剂。
实施例3
将6600克氢氧化铝干胶粉(同上)，和4000克碱式碳酸锌粉(同上)，经湿法混合均匀，经小型捏合机捏合后，挤条、切粒并整型成Φ4毫米的球形，再在糖衣机上涂敷3000克铝溶胶(同上)与1700克氯化钙粉(同上)以及去离子水的混合物料，成型后的物料在工业烘箱中120℃干燥3小时后，采用分步多次浸渍、干燥的方法将5000克硝酸铜(同上)、400克富铈氯化稀土(同上)、200克硝酸(同上)和去离子水的混合溶液浸渍到复合载体上，干燥条件是120℃下干燥2小时，再在工业马弗炉中330℃下焙烧活化10小时，制备成实施例3的脱砷吸附剂。
实施例4
将实施例1～3和比较例1～2的脱砷吸附剂在微型评价装置上做吸附脱砷性能测试。测试条件为常温、常压、空速为1600～1800小时 -1，脱砷剂装量为20毫升，原料为某化工厂的工业用丙烯原料，其纯度>≥99.5％、砷含量为1600～1800ng/g、硫含量为<18mg/m 3、水含量<50μg/g。当出口砷含量>10ng/g时停止吸附反应过程，作为1个测试操作周期，试验所得结果列于下表1中。
表1、实施例1～3和比较例1～2的脱砷吸附剂对比情况
Figure PCTCN2020118768-appb-000001
从表1的对比数据可以看出，本发明的实施例样品具有更好的脱砷精度和吸附脱砷容量。同时，本发明的脱砷吸附剂在这种杂质含量较高的工况下使用过程中，具备更优的竞争吸附选择性和使用强度性能。
最后需要说明的是，以上实施例仅用于说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而未脱离本发明技术方案的精神和范围。

Claims (10)

  1. 一种脱砷吸附剂，其特征是以占吸附剂总量计的组成中含有：10～40wt％的CuO、5～30wt％的ZnO、1～20wt％的CaO、0.1～10wt％的Cl -、0.1～10wt％的稀土氧化物和余量的Al 2O 3，复合载体由大孔γ-Al 2O 3、纳米ZnO组合物形成的高孔容内核，和CaCl 2、Al 2(OH) nCl 6-n组合物涂覆形成的外层所共同构成，其中n为1～5；复合载体浸渍铜化合物、稀土组合物的酸化溶液后干燥、焙烧活化；得到的脱砷吸附剂的孔容为0.1～0.9毫升/克，应用于丙烯的脱砷吸附净化过程。
  2. 根据权利要求1所述的一种脱砷吸附剂，其特征在于，所述的Al 2(OH) nCl 6-n中的n为4.0～4.8。
  3. 根据权利要求1所述的一种脱砷吸附剂，其特征在于，所述的铜化合物是酒石酸铜、氧化铜、氢氧化铜、碳酸铜、硫酸铜、硝酸铜、醋酸铜、氯化铜中的一种或多种。
  4. 根据权利要求1所述的一种脱砷吸附剂，其特征在于，所述的稀土组合物是镧、铈的化合物或富镧、富铈的混合物。
  5. 根据权利要求1所述的一种脱砷吸附剂，其特征在于，所述的酸化溶液是经硝酸酸化后得到的溶液。
  6. 根据权利要求1所述的一种脱砷吸附剂，其特征在于，所述的脱砷吸附剂的孔容为0.3～0.7毫升/克。
  7. 一种脱砷吸附剂的制备方法，其特征为制备过程包括如下步骤：
    (1)将大孔γ-Al 2O 3、纳米ZnO的前驱体组合物采用选自干法、湿法、液相混合法中的一种混合均匀，并选用滚球、油柱成型、挤条-切粒-整型方式中的一种，将混合物料制备成小球型；
    (2)将成型后的物料在100～250℃下干燥0.5～15小时，制备成复合载体 内核；
    (3)将小球型内核在滚球机内将CaCl 2、Al 2(OH) nCl 6-n组合物涂覆在外层上构成复合载体，其中，n为1～5；
    (4)采用分步、混合浸渍方法中的一种，浸渍铜化合物和稀土组合物的酸化溶液，100～250℃下干燥0.5～15小时，浸渍、干燥步骤可交替重复1～5次；
    (5)干燥后的物料经300～650℃下焙烧活化0.5～15小时。
  8. 根据权利要求7所述的一种脱砷吸附剂的制备方法，其特征在于所述的大孔γ-Al 2O 3的前驱体为硫酸铝法制备的氢氧化铝干凝胶粉，焙烧后形成的大孔γ-Al 2O 3孔容为0.4～1.2毫升/克。
  9. 根据权利要求7所述的一种脱砷吸附剂的制备方法，其特征在于所述的纳米ZnO前驱体是碱式碳酸锌。
  10. 根据权利要求7所述的一种脱砷吸附剂的制备方法，其特征在于所述的焙烧活化条件为350～500℃下焙烧活化1～5小时。
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