WO2018161949A1 - 加氢处理催化剂浸渍溶液及其制备方法 - Google Patents

加氢处理催化剂浸渍溶液及其制备方法 Download PDF

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WO2018161949A1
WO2018161949A1 PCT/CN2018/078514 CN2018078514W WO2018161949A1 WO 2018161949 A1 WO2018161949 A1 WO 2018161949A1 CN 2018078514 W CN2018078514 W CN 2018078514W WO 2018161949 A1 WO2018161949 A1 WO 2018161949A1
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containing compound
carbonate
nickel
temperature
hydrotreating catalyst
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English (en)
French (fr)
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王杰华
石友良
冯春峰
张然
许莉
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武汉凯迪工程技术研究总院有限公司
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Publication of WO2018161949A1 publication Critical patent/WO2018161949A1/zh

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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0213—Preparation of the impregnating solution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Definitions

  • the invention relates to an impregnation solution, in particular to a hydrotreating catalyst impregnation solution and a preparation method thereof.
  • the hydrotreating catalysts used in the industry usually carry inorganic hydrogen oxides (such as alumina, silica, alumina-silica, etc.) as carriers and carry some hydrogenation active metal components in a certain manner (generally It is a Group VIB metal and a Group VIII metal such as Mo, W and Ni, Co, etc.).
  • inorganic hydrogen oxides such as alumina, silica, alumina-silica, etc.
  • some hydrogenation active metal components in a certain manner generally It is a Group VIB metal and a Group VIII metal such as Mo, W and Ni, Co, etc.
  • Common methods for supporting the active metal component include a dipping method, a kneading method, and the like. In view of the high hydrogenation activity and the full utilization of the active metal, the preparation of the hydrogenation catalyst by the impregnation method is extensive.
  • the nature of the impregnation solution is critical when preparing the hydrogenation catalyst by impregnation.
  • the pH of the impregnation solution has a large effect on the structure, dispersion and interaction of the active metal (e.g., Mo) on the surface of the catalyst with a support such as Al 2 O 3 .
  • the active metal e.g., Mo
  • the first type is an alkaline solution of Group VIB and Group VIII elements, such as an aqueous ammonia solution containing both molybdenum and cobalt (nickel).
  • the impregnation solution is alkaline. If it is to be impregnated once to form a catalyst, it needs to be formulated to a high concentration. Molybdenum-cobalt (nickel)-ammonia solution, which is unstable, causes difficulties in the impregnation operation, and it is difficult to prepare a high metal content catalyst with such an impregnation solution in a single load.
  • the second type is an acidic solution of Group VIB and Group VIII elements, such as a Mo-Ni-P impregnation solution.
  • a Mo-Ni-P impregnation solution such as a Mo-Ni-P impregnation solution.
  • the phosphoric acid is mixed with the molybdenum salt and the nickel salt in a certain ratio, and heated under reflux to finally obtain a Mo-Ni-P solution.
  • Most of the hydrotreating catalysts use ⁇ -Al 2 O 3 as the carrier, and the isoelectric point is 7-9, while the pH of the Mo-Ni-P immersion liquid is generally below 2, and the too low pH value will not only make the specific surface area of the carrier. Loss occurs during the impregnation process to reduce the specific surface area of the catalyst; it also causes the active component to interact too strongly with the support, which reduces the dispersibility of the active metal, resulting in a decrease in the activity of the hydrotreating catalyst.
  • the industry has added a basic nitrogen-containing compound (for example, an aqueous ammonia solution) to the acidic immersion liquid to change the pH between 2 and 6.
  • a basic nitrogen-containing compound for example, an aqueous ammonia solution
  • the pH of the impregnation solution can be increased, a large amount of the nitrogen-containing compound is added when the pH of the solution is adjusted, so that the active metal content in the impregnation solution is greatly reduced. Therefore, when the impregnation solution is prepared by the method and a high-load hydrogenation catalyst is prepared, the initial active metal content of the impregnation solution is too high to be easily realized.
  • the object of the present invention is to provide a hydrotreating catalyst impregnation solution with high active metal content, good stability, high pH and adjustable, and a preparation method thereof.
  • the hydrotreating catalyst impregnation solution provided by the present invention is configured as an aqueous solution from a molybdenum-containing compound, a nickel-containing compound, a phosphorus-containing compound, and a carbonate.
  • the concentration of the molybdenum-containing compound is 10 to 80 g/100 ml in terms of MoO 3 ; the concentration of the nickel-containing compound is 1 to 15 g/100 ml in terms of NiO; and the concentration of the phosphorus-containing compound is 0.5 to 5 g in terms of P element. 100 ml; carbonate concentration is 0.2 to 5.0 g/100 ml, and the pH of the solution is 2 to 6.
  • the concentration of the molybdenum-containing compound is 15 to 55 g/100 ml in terms of MoO 3 ; the concentration of the nickel-containing compound is 5 to 12 g/100 ml in terms of NiO; and the concentration of the phosphorus-containing compound is 0.8 to 2.0 g in terms of P element. /100 ml; carbonate concentration is 0.8 to 3.2 g / 100 ml.
  • the carbonate is an alkali metal carbonate or acid salt, or an ammonium carbonate or acid salt, more preferably (NH 4 ) 2 CO 3 .
  • the molybdenum-containing compound is one or more of molybdenum oxide, ammonium molybdate, and ammonium paramolybdate;
  • the nickel-containing compound is nickel nitrate, nickel acetate, basic nickel carbonate, nickel carbonate, and chlorination.
  • the phosphorus-containing compound is one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate, and disodium hydrogen phosphate.
  • the molybdenum-containing compound is molybdenum oxide
  • the nickel-containing compound is basic nickel carbonate
  • the phosphorus-containing compound is phosphoric acid.
  • the preparation method of the above hydrotreating catalyst impregnation solution comprises the following steps:
  • step 2 heating in two steps, the first step is heated to a temperature of 35 to 60 ° C, and the temperature is constant for 0 to 1.5 h; the second step is continued to increase the temperature to 90 to 110 ° C, and the temperature is refluxed for 0 to 3 h, so that step 1) The solute added in the solution is completely dissolved, and the dark green clear transparent solution is obtained;
  • step 2) carbonate is added to adjust the pH of the impregnation solution to 2-6.
  • the first step is heated to a temperature of 40 to 50 ° C, and the temperature is reacted for 0.5 to 1 hour; the second step is continued to raise the temperature to a temperature of 90 to 100 ° C, and the temperature is refluxed for 1 to 2 hours.
  • the carbonate is added after the first step of constant temperature or after the second step of constant temperature.
  • the invention has the beneficial effects that the Mo-Ni-P impregnating liquid provided has high metal content; the property is stable and can be stored for a long time; the pH value of the solution is high and adjustable; when the hydrogenation catalyst is prepared by impregnation, the active metal is on the carrier.
  • the dispersion is uniform, the force is moderate, the specific surface area and pore volume are large, and the catalyst activity is high.
  • This comparative example describes a method of preparing a Mo-Ni-P immersion liquid according to a conventional method.
  • 9.3 g of phosphoric acid (mass concentration: 85.0%) and 150 ml of water were mixed and added to a three-necked flask, and 105.1 g of molybdenum trioxide (industrial grade) and basic nickel carbonate (44.0 wt% by weight of Ni) were added while stirring, and the temperature was raised to 40 to 50 ° C, the reaction was 0.5 h, the temperature was raised to 90-100 ° C, the reaction was stopped for 1 h, the heating was stopped, and after cooling to room temperature, the obtained solution was filtered to a volume of 250 ml to obtain a dark green clear transparent solution A. The pH of the solution was measured to be 2.63.
  • This embodiment describes a method of adding ammonium carbonate to adjust the pH of the solution to about 4 during the preparation of the Mo-Ni-P impregnation liquid.
  • 9.3 g of phosphoric acid (mass concentration: 85.0%) and 150 ml of water were mixed and added to a three-necked flask, and 105.1 g of molybdenum trioxide (industrial grade) and basic nickel carbonate (44.0 wt% by weight of Ni) were added while stirring, and the temperature was raised to 40 ⁇ 50°C, reaction 0.5h, slowly add 3.0g ammonium carbonate (40.0% by weight of NH 3 ), raise the temperature to 90-100 ° C, react for 1h, stop heating, cool to room temperature, then filter the solution to a constant volume To 250ml, the dark green clear clear solution A 1 is obtained. The pH of the solution was measured to be 4.07.
  • This embodiment describes a method of adding ammonium carbonate to adjust the pH of the solution to about 5 during the preparation of the Mo-Ni-P impregnation liquid.
  • 9.3 g of phosphoric acid (mass concentration: 85.0%) and 150 ml of water were mixed and added to a three-necked flask, and 105.1 g of molybdenum trioxide (industrial grade) and basic nickel carbonate (44.0 wt% by weight of Ni) were added while stirring, and the temperature was raised to 40 ⁇ 50°C, reaction 0.5h, slowly add 5.1g ammonium carbonate (40.0% by weight of NH 3 ), raise the temperature to 90 ⁇ 100° C., react for 1h, stop heating, cool to room temperature, then filter the solution. To 250 ml, the dark green clear solution A 2 was obtained . The pH of the solution was measured to be 5.10.
  • This embodiment describes a method of adding ammonium carbonate to adjust the pH of the solution to about 6 during the preparation of the Mo-Ni-P impregnation solution.
  • 9.3 g of phosphoric acid (mass concentration: 85.0%) and 150 ml of water were mixed and added to a three-necked flask, and 105.1 g of molybdenum trioxide (industrial grade) and basic nickel carbonate (44.0 wt% by weight of Ni) were added while stirring, and the temperature was raised to 40 ⁇ 50°C, reaction 0.5h, slowly add 8.0g ammonium carbonate (40.0% by weight of NH 3 ), raise the temperature to 90-100 ° C, react for 1h, stop heating, cool to room temperature, then filter the solution, to volume To 250 ml, the dark green clear solution A 3 was obtained .
  • the pH of the solution was measured to be 6.02.
  • This test example lists the composition and main properties of A, A 1 , A 2 , and A 3 solutions, and compares the A series solutions. See Table 1 for details.
  • This comparative example describes a method of preparing a Mo-Ni-P immersion liquid according to a conventional method.
  • 14.0 g of phosphoric acid (mass concentration: 85.0%) and 150 ml of water were mixed and added to a three-necked flask, and 125.0 g of molybdenum trioxide (industrial grade) and basic nickel carbonate (44.0 wt% by weight of Ni) were added thereto while stirring, and the temperature was raised to 40 to 50 ° C, the reaction was 0.5 h, the temperature was raised to 90-100 ° C, the reaction was stopped for 1 h, the heating was stopped, and after cooling to room temperature, the obtained solution was filtered to a volume of 250 ml to obtain a dark green clear transparent solution B. The pH of the solution was measured to be 2.3.
  • This example describes the method of adjusting the pH of the impregnation solution to about 4 by adding ammonium carbonate to the solution B prepared in Comparative Example 2.
  • 50 ml of solution B was placed in a beaker, and under constant stirring, ammonium carbonate (40.0% by weight in terms of NH 3 ) was slowly added to control the rate of addition.
  • the pH value of the solution was measured in time by a pH meter.
  • the pH was 4.0, the addition of ammonium carbonate was stopped, and thus the amount of ammonium carbonate added was 0.4 g, and stirring was continued until the solution was uniformly stabilized to obtain a solution B 1 .
  • This example describes the method of adjusting the pH of the impregnation solution to about 5 by adding ammonium carbonate to the solution B prepared in Comparative Example 2.
  • 50 ml of solution B was placed in a beaker, and under constant stirring, ammonium carbonate (40.0% by weight in terms of NH 3 ) was slowly added to control the rate of addition.
  • the pH value of the solution was measured in time by a pH meter.
  • the pH was 5.0, the addition of ammonium carbonate was stopped, and thus the amount of ammonium carbonate added was 0.7 g, and stirring was continued until the solution was uniformly stabilized to obtain a solution B 2 .
  • This example describes the method of adjusting the pH of the impregnation solution to about 6 by adding ammonium carbonate to the solution B prepared in Comparative Example 2.
  • 50 ml of solution B was placed in a beaker, and under constant stirring, ammonium carbonate (40.0% by weight in terms of NH 3 ) was slowly added to control the rate of addition.
  • the pH value of the solution was measured in time by a pH meter.
  • the pH was 6.0, the addition of ammonium carbonate was stopped, and thus the amount of ammonium carbonate added was 1.2 g, and stirring was continued until the solution was uniformly stabilized to obtain a solution B 3 .
  • the Mo-Ni-P solution can be prepared by a conventional method, and then the impregnation solution of different pH is prepared by adjusting the amount of ammonium carbonate added, and the metal content is high and the solution property is stable.
  • This test example describes the preparation of the catalyst carrier. Weighed 275 g of large-hole pseudo-boehmite (Yantai Henghui Chemical Co., Ltd., specific surface 350 m 2 /g, pore volume 0.92 ml/g, dry basis 72.8%), and added citric acid (Hubei 798 Chemical) 6 g.
  • This test example describes a method of preparing a catalyst using the impregnation liquids of Examples 1 to 6.
  • the prepared carrier Z 1 was separately impregnated with the solutions A 1 , A 2 , A 3 , B 1 , B 2 and B 3 , and dried at 110 ° C for 2 h and at 460 ° C for 3 h to obtain the catalyst CA 1 .
  • CA 2 , CA 3 , CB 1 , CB 2 , CB 3 The prepared carrier Z 1 was separately impregnated with the solutions A 1 , A 2 , A 3 , B 1 , B 2 and B 3 , and dried at 110 ° C for 2 h and at 460 ° C for 3 h to obtain the catalyst CA 1 . , CA 2 , CA 3 , CB 1 , CB 2 , CB 3 .
  • This test example describes a method for preparing a catalyst using the impregnation liquid in Comparative Examples 1 and 2.
  • the prepared carrier Z 1 was separately impregnated with the solutions A and B, and dried at 110 ° C for 2 h and at 460 ° C for 3 h to obtain catalysts DA and DB.
  • This test example is a catalyst activity evaluation test.
  • the catalyst activity evaluation test was carried out on a small 30 ml apparatus, and the catalyst was pre-vulcanized before the activity evaluation.
  • the catalyst evaluation conditions were a total reaction pressure of 8.0 MPa, a volume space velocity of 1.0 h -1 , a hydrogen oil ratio of 1000:1, and a reaction temperature of 380 °C.
  • the properties of the raw material oil for the activity evaluation test are shown in Table 4, and the results of the activity evaluation are shown in Table 5.
  • the specific surface area and pore volume of the catalyst prepared by the present invention are improved by the specific method, the pH is higher and the pH is adjustable, the active metal content is high, and the stability is good. Both hydrodesulfurization and hydrodenitrogenation performance have been greatly improved.

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Abstract

一种加氢处理催化剂浸渍溶液及其制备方法，该浸渍溶液是由含钼化合物、含镍化合物、含磷化合物和碳酸盐配置成的水溶液。其制备方法包括如下步骤：1)向水中加入含钼化合物、含镍化合物、含磷化合物，混合均匀；2)采用两步加热升温，第一步升温至温度35～60℃，并恒温反应0～1.5h；第二步继续升温至温度90～110℃，并恒温回流0～3h，使步骤1)中加入的溶质全部溶解，得墨绿澄清透明溶液；步骤2)中，加入碳酸盐，调节浸渍溶液的pH至2～6。该浸渍溶液金属含量较高；性质稳定，可长期存放，溶液pH值较高且可调，制成的催化剂活性较高。

Description

加氢处理催化剂浸渍溶液及其制备方法 技术领域
本发明涉及一种浸渍溶液，特别是指一种加氢处理催化剂浸渍溶液及其制备方法。
背景技术
目前，工业上所用的加氢处理催化剂，通常是以无机氧化物(如氧化铝、二氧化硅、氧化铝-二氧化硅等)为载体，按一定方式负载一些加氢活性金属组分(一般为ⅥB族金属和Ⅷ族金属，如Mo、W和Ni、Co等)。常见的负载活性金属组分的方法有浸渍法、混捏法等。考虑到高加氢活性以及对活性金属的充分利用，使用浸渍法制备加氢催化剂较为广泛。
用浸渍法制备加氢催化剂时，浸渍溶液的性质至关重要。特别是浸渍溶液pH值对催化剂表面上活性金属(如Mo)的结构、分散度及其与载体(如Al 2O 3)的相互作用有很大影响。根据pH值的不同，目前常用的加氢处理催化剂浸渍溶液有两种类型：
第一类为ⅥB族、Ⅷ族元素的碱性溶液，例如同时含有钼和钴(镍)的氨水溶液，此浸渍溶液为碱性，如果要一次浸渍制成催化剂，需要配成浓度很高的钼-钴(镍)-氨溶液，这种溶液不稳定，给浸渍操作带来困难，很难用这种浸渍溶液一次性负载制备高金属含量催化剂。
第二类为ⅥB族、Ⅷ族元素的酸性溶液，例如Mo-Ni-P浸渍溶液，制备时将磷酸与钼盐及镍盐以一定比例混合，加热回流，最终制得Mo-Ni-P溶液。加氢处理催化剂大多以γ-Al 2O 3为载体，其等电点为7～9，而Mo-Ni-P浸渍液的pH一般在2以下，过低的pH值不仅会使载体比表面积在浸渍过程中产生损失从而使催化剂比表面积有所降低；还会引起活性组分与载体相互作用过强，使活性金属分散性降低，导致加氢处理催化剂的活性降低。
针对Mo-Ni-P浸渍液pH偏低的问题，行业中有在酸性浸渍液中添加碱性含氮化合物(例如氨水溶液)，使其pH值在2～6之间变化。这样虽然可以使浸渍溶液pH提高，但在调整溶液pH时加入大量的含氮化合物，使浸渍溶液中活性金属含量大大降低。因此，利用该方法制备浸渍溶液并制备高负载量加氢催化剂时，对于浸渍溶液初始活性金属含量要求过高，不易实现。
发明内容
本发明的目的在于提供一种活性金属含量高、稳定性好、pH较高且可调的加氢处理催化剂浸渍溶液及其制备方法。
为实现上述目的，本发明所提供的加氢处理催化剂浸渍溶液由含钼化合物、含镍化合物、含磷化合物和碳酸盐配置成水溶液。
优选地，所述水溶液中，含钼化合物浓度以MoO 3计为10～80g/100ml；含镍化合物浓度以NiO计为1～15g/100ml；含磷化合物浓度以P元素计为0.5～5g/100ml；碳酸盐浓度为0.2～5.0g/100ml，所述溶液的pH为2～6。
进一步地，所述水溶液中，含钼化合物浓度以MoO 3计为15～55g/100ml；含镍化合物浓度以NiO计为5～12g/100ml；含磷化合物浓度以P元素计为0.8～2.0g/100ml；碳酸盐浓度为0.8～3.2g/100ml。
优选地，所述碳酸盐为碱金属的碳酸正盐或酸式盐，或者铵的碳酸正盐或酸式盐，更优为(NH 4) 2CO 3。
优选地，所述含钼化合物为氧化钼、钼酸铵、仲钼酸铵中的一种或几种；所述含镍化合物为硝酸镍、醋酸镍、碱式碳酸镍、碳酸镍、氯化镍中的一种或几种；所述含磷化合物为磷酸、磷酸二氢铵、磷酸氢二铵、磷酸二氢钠及磷酸氢二钠中的一种及几种。
优选地，所述含钼化合物为氧化钼，所述含镍化合物为碱式碳酸镍，所述含磷化合物为磷酸。
上述加氢处理催化剂浸渍溶液的制备方法，包括如下步骤：
1)向水中加入含钼化合物、含镍化合物、含磷化合物，混合均匀；
2)采用两步加热升温，第一步升温至温度35～60℃，并恒温反应0～1.5h；第二步继续升温至温度90～110℃，并恒温回流0～3h，使步骤1)中加入的溶质全部溶解，得墨绿澄清透明溶液；
步骤2)中，加入碳酸盐，调节浸渍溶液的pH至2～6。
优选地，步骤2)中，第一步升温至温度40～50℃，并恒温反应0.5～1h；第二步继续升温至温度90～100℃，并恒温回流1～2h。
优选地，所述碳酸盐在第一步恒温后或第二步恒温后加入。
本发明的有益效果是：所提供的Mo-Ni-P浸渍液金属含量较高；性质稳定，可长期 存放；溶液pH值较高且可调；浸渍制备加氢催化剂时，活性金属在载体上分散均匀，作用力适中，比表面积及孔容较大，催化剂活性较高。
具体实施方式
下面通过具体实施例对本发明作进一步的详细说明。
对比例1
本对比例介绍按常规方法制备Mo-Ni-P浸渍液方法。取9.3g磷酸(质量浓度85.0％)与150ml水混合加入三口烧瓶，在搅拌中加入三氧化钼(工业级)105.1g和碱式碳酸镍(以Ni计，44.0重量％)29.4g，升温至40～50℃，反应0.5h，升温至90～100℃，反应1h，停止加热，冷却至室温后对所得溶液过滤，定容至250ml，即得墨绿色澄清透明溶液A。测溶液pH为2.63。
实施例1
本实施例介绍在Mo-Ni-P浸渍液制备过程中加入碳酸铵调节溶液pH至4左右方法。取9.3g磷酸(质量浓度85.0％)与150ml水混合加入三口烧瓶，在搅拌中加入三氧化钼(工业级)105.1g和碱式碳酸镍(以Ni计，44.0重量％)29.4g，升温至40～50℃，反应0.5h，缓慢加入3.0g碳酸铵(以NH 3计，40.0重量％)，升温至90～100℃，反应1h，停止加热，冷却至室温后对所得溶液过滤，定容至250ml，即得墨绿色澄清透明溶液A 1。测溶液pH为4.07。
实施例2
本实施例介绍在Mo-Ni-P浸渍液制备过程中加入碳酸铵调节溶液pH至5左右方法。取9.3g磷酸(质量浓度85.0％)与150ml水混合加入三口烧瓶，在搅拌中加入三氧化钼(工业级)105.1g和碱式碳酸镍(以Ni计，44.0重量％)29.4g，升温至40～50℃，反应0.5h，缓慢加入5.1g碳酸铵(以NH 3计，40.0重量％)，升温至90～100℃，反应1h，停止加热，冷却至室温后对所得溶液过滤，定容至250ml，即得墨绿色澄清透明溶液A 2。测溶液pH为5.10。
实施例3
本实施例介绍在Mo-Ni-P浸渍液制备过程中加入碳酸铵调节溶液pH至6左右方法。取9.3g磷酸(质量浓度85.0％)与150ml水混合加入三口烧瓶，在搅拌中加入三氧化钼(工业级)105.1g和碱式碳酸镍(以Ni计，44.0重量％)29.4g，升温至40～50℃， 反应0.5h，缓慢加入8.0g碳酸铵(以NH 3计，40.0重量％)，升温至90～100℃，反应1h，停止加热，冷却至室温后对所得溶液过滤，定容至250ml，即得墨绿色澄清透明溶液A 3。测溶液pH为6.02。
试验例1
本试验例列出A、A 1、A 2、A 3溶液组成及主要性质，并对A系列溶液做出对比，具体见表1。
表1溶液A系列组成及主要性质对比
Figure PCTCN2018078514-appb-000001
由表1可知，在Mo-Ni-P溶液制备过程中，可以通过调节碳酸铵加入量，制备得到不同pH浸渍溶液，且金属含量较高，溶液性质稳定。
对比例2
本对比例介绍按常规方法制备Mo-Ni-P浸渍液方法。取14.0g磷酸(质量浓度85.0％)与150ml水混合加入三口烧瓶，在搅拌中加入三氧化钼(工业级)125.0g和碱式碳酸镍(以Ni计，44.0重量％)33.6g，升温至40～50℃，反应0.5h，升温至90～100℃，反应1h，停止加热，冷却至室温后对所得溶液过滤，定容至250ml，即得墨绿色澄清透明溶液B。测溶液pH为2.3。
实施例4
本实施例介绍用对比例2中所制备溶液B加入碳酸铵调节浸渍溶液pH至4左右方法。取50ml溶液B放入烧杯，在不断搅拌条件下，缓慢加入碳酸铵(以NH 3计，40.0重量％)，控制加入速度。通过pH计及时测量溶液pH值，当pH为4.0时停止加入碳酸铵，至此碳酸铵加入量为0.4g，继续搅拌至溶液均匀稳定，得溶液B 1。
实施例5
本实施例介绍用对比例2中所制备溶液B加入碳酸铵调节浸渍溶液pH至5左右方法。取50ml溶液B放入烧杯，在不断搅拌条件下，缓慢加入碳酸铵(以NH 3计，40.0重量％)，控制加入速度。通过pH计及时测量溶液pH值，当pH为5.0时停止加入碳酸铵，至此碳酸铵加入量为0.7g，继续搅拌至溶液均匀稳定，得溶液B 2。
实施例6
本实施例介绍用对比例2中所制备溶液B加入碳酸铵调节浸渍溶液pH至6左右方法。取50ml溶液B放入烧杯，在不断搅拌条件下，缓慢加入碳酸铵(以NH 3计，40.0重量％)，控制加入速度。通过pH计及时测量溶液pH值，当pH为6.0时停止加入碳酸铵，至此碳酸铵加入量为1.2g，继续搅拌至溶液均匀稳定，得溶液B 3。
试验例2
本试验例列出B、B 1、B 2、B 3溶液组成及主要性质，并对B系列溶液做出对比，具体见表2。
表2溶液B系列组成及主要性质对比
Figure PCTCN2018078514-appb-000002
由表2可知，可以用常规方法制备Mo-Ni-P溶液，然后通过调节碳酸铵加入量，制备得到不同pH浸渍溶液，且金属含量较高，溶液性质稳定。
试验例3
本试验例介绍催化剂载体制备方式。称取大孔拟薄水铝石(烟台恒辉化工有限公司，比表面350m 2/g，孔容0.92ml/g，干基72.8％)275g，加入柠檬酸(湖北七八九化工)6g，田菁粉(武汉陌兴生物科技有限公司)4g，加入8.80g HNO 3(65～68wt％)、7.2g H 3BO 3(99.5wt％)和220ml H 2O混合均匀溶液，碾压20min，用两叶最大间距1.6mm三叶草孔板挤条成型，120℃干燥4h，500℃焙烧4h。焙烧后载体记为Z 1。
试验例4
本试验例介绍用实施例1～6中浸渍液制备催化剂方法。取所制备载体Z 1，分别用溶液A 1、A 2、A 3、B 1、B 2、B 3进行等体积浸渍，浸渍完成后110℃干燥2h，460℃焙烧3h，制得催化剂CA 1、CA 2、CA 3、CB 1、CB 2、CB 3。
试验例5
本试验例介绍用对比例1、2中浸渍液制备催化剂方法。取所制备载体Z 1，分别用溶液A、B进行等体积浸渍，浸渍完成后110℃干燥2h，460℃焙烧3h，制得催化剂DA、DB。
试验例6
本试验例列出上述制备催化剂主要性质，具体见表3。
表3制备催化剂主要性质
Figure PCTCN2018078514-appb-000003
试验例7
本试验例为催化剂活性评价试验。催化剂活性评价试验在30ml小型装置上进行，活性评价前需要对催化剂进行预硫化。催化剂评价条件为在反应总压8.0MPa，体积空速1.0h -1，氢油比1000：1，反应温度380℃。活性评价试验用原料油性质见表4，活性评价结果见表5。
表4原料油性质
原料油 伊朗VGO
密度(20℃)，g·cm -3 0.9168
馏程，℃  
IBP 336
EBP 542
S，％ 1.59
N，ppm 1681
表5活性评价结果
Figure PCTCN2018078514-appb-000004
由上表可知，本发明通过用特定方法所制备的pH较高且可调、活性金属含量高、稳定性好浸渍溶液，制备得到的催化剂比表面积和孔容都有所提高，对于该催化剂的加氢脱硫与加氢脱氮性能都有较大的提升。

Claims (10)

  1. 一种加氢处理催化剂浸渍溶液，其特征在于：由含钼化合物、含镍化合物、含磷化合物和碳酸盐配置成水溶液。
  2. 根据权利要求1所述的加氢处理催化剂浸渍溶液，其特征在于：所述水溶液中，含钼化合物浓度以MoO 3计为10～80g/100ml；含镍化合物浓度以NiO计为1～15g/100ml；含磷化合物浓度以P元素计为0.5～5g/100ml；碳酸盐浓度为0.2～5.0g/100ml，所述溶液的pH为2～6。
  3. 根据权利要求2所述的加氢处理催化剂浸渍溶液，其特征在于：所述水溶液中，含钼化合物浓度以MoO 3计为15～55g/100ml；含镍化合物浓度以NiO计为5～12g/100ml；含磷化合物浓度以P元素计为0.8～2.0g/100ml；碳酸盐浓度为0.8～3.2g/100ml。
  4. 根据权利要求1～3中任一项所述的加氢处理催化剂浸渍溶液，其特征在于：所述碳酸盐为碱金属的碳酸正盐或酸式盐，或者铵的碳酸正盐或酸式盐。
  5. 根据权利要求4所述的加氢处理催化剂浸渍溶液，其特征在于：所述碳酸盐为(NH 4) 2CO 3。
  6. 根据权利要求1～3中任一项所述的加氢处理催化剂浸渍溶液，其特征在于：所述含钼化合物为氧化钼、钼酸铵、仲钼酸铵中的一种或几种；所述含镍化合物为硝酸镍、醋酸镍、碱式碳酸镍、碳酸镍、氯化镍中的一种或几种；所述含磷化合物为磷酸、磷酸二氢铵、磷酸氢二铵、磷酸二氢钠及磷酸氢二钠中的一种及几种。
  7. 根据权利要求6所述的加氢处理催化剂浸渍溶液，其特征在于：所述含钼化合物为氧化钼，所述含镍化合物为碱式碳酸镍，所述含磷化合物为磷酸。
  8. 根据权利要求1～3中任一项所述的加氢处理催化剂浸渍溶液的制备方法，其特征在于，包括如下步骤：
    1)向水中加入含钼化合物、含镍化合物、含磷化合物，混合均匀；
    2)采用两步加热升温，第一步升温至温度35～60℃，并恒温反应0～1.5h；第二步继续升温至温度90～110℃，并恒温回流0～3h，使步骤1)中加入的溶质全部溶解，得墨绿澄清透明溶液；
    步骤2)中，加入碳酸盐，调节浸渍溶液的pH至2～6。
  9. 根据权利要求8所述的加氢处理催化剂浸渍溶液的制备方法，其特征在于：步骤2)中，第一步升温至温度40～50℃，并恒温反应0.5～1h；第二步继续升温至温度90～100℃，并恒温回流1～2h。
  10. 根据权利要求8所述的加氢处理催化剂浸渍溶液的制备方法，其特征在于：所述碳酸盐在第一步恒温后或第二步恒温后加入。
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