CN100577288C - A kind of hydrogenation active protection agent and preparation method thereof - Google Patents

Abstract

Translated fromChinese

一种加氢保护剂及其制备，该保护剂含有一种或几种多孔的耐热无机氧化物，其特征在于，所述保护剂总的孔容为0.3-1.5毫米/克，其中含有毫米级大孔，毫米级大孔孔直径为0.1～1.5微米，毫米级大孔孔容为0.05～0.7毫升/克。所述加氢保护剂的制备方法，包括将一种或几种多孔的耐热无机氧化物和/或多孔的耐热无机氧化物的前身物与至少一种有机物混合、成型、干燥并焙烧，其中，所述有机化合物为熔点介于30～200℃、粒径0.3～2.5毫米且不溶于水的固体颗粒。与现有技术提供的加氢保护剂相比，本发明提供的加氢保护剂可以容纳更多的金属杂质或颗粒物，由此可有效保护加氢主剂，延长主剂的使用寿命。A hydrogenation protective agent and its preparation, the protective agent contains one or more porous heat-resistant inorganic oxides, characterized in that the total pore volume of the protective agent is 0.3-1.5 mm/g, which contains mm The diameter of the millimeter-scale macropores is 0.1-1.5 microns, and the volume of the millimeter-scale macropores is 0.05-0.7 ml/g. The preparation method of the hydrogenation protecting agent comprises mixing one or more porous heat-resistant inorganic oxides and/or precursors of porous heat-resistant inorganic oxides with at least one organic substance, forming, drying and roasting, Wherein, the organic compound is a water-insoluble solid particle with a melting point between 30-200° C. and a particle size of 0.3-2.5 mm. Compared with the hydrogenation protection agent provided by the prior art, the hydrogenation protection agent provided by the present invention can accommodate more metal impurities or particles, thereby effectively protecting the hydrogenation main agent and prolonging the service life of the main agent.

Description

A kind of hydrogenation activity protective agent and preparation method thereof

Technical field

The invention relates to a kind of hydrogenation protecting agent and preparation thereof, more specifically say so about the hydrogenation protecting agent and the preparation thereof of the higher feedstock oil of a kind of Fe of processing, Ca or particle content.

Background technology

The shut-down of hydrogenation plant has sayed that from technological layer many reasons cause, but main be relevant with catalysqt deactivation and big bed pressure drop.

Catalysqt deactivation also has many factors, and one of them is to be caused in the deposition of catalyst surface by metal impurities in the raw material such as Fe, Ca.The increase of beds pressure drop is also relevant with many factors, the most important thing is that dirty thing, particle in the feedstock oil is deposited between the catalyst granules and the carbon deposit of catalyst particles intergranular etc. causes.

Many hydrotreated feed oil; especially contain a large amount of Fe in the residual oil; the Ca organic compound; these compounds reaction speed in hydrogenation process is very fast; for general catalyst for demetalation or protective agent; Fe and Ca are deposited between catalyst outer surface and the catalyst granules with the form of sulfide; cause the catalyst aperture to stop up and inactivation; cause the rising of bed pressure drop simultaneously; especially contain the oil-soluble organic compound of Fe and sulphur under the residual hydrogenation condition; generate gluey iron sulfide immediately in case run into hydrogen; these gluey iron sulfide adhere to or sticking being associated between catalyst outer surface and the catalyst granules; add the generation that iron sulfide also impels coking to react simultaneously, more aggravated the deactivation rate of catalyst and gathering way of pressure drop.It is not obvious to utilize conventional protective agent and catalyst for demetalation to remove these metal impurities effects.

In addition, particle in the feedstock oil of hydrotreatment (by comprising that colloid and coke precursor form) deposits at the catalyst particles intergranular, cause that mainly bed pressure drop rises, and mainly occur in the reactor head that raw material contacts at first, and owing to a part in the particle is the iron content particle, for decompression residuum, these iron are to exist with the iron sulfide form basically, after being deposited on catalyst surface, play autocatalysis as mentioned above, encourage green coke, thereby aggravated the pressure drop rising, therefore often cause the device shut-down and carry out " casting aside the top ", change the reactor head catalyst, this shut-down has greatly influenced the benefit of whole refinery.

For both of these case; all be badly in need of a kind of special protection catalyst that is contained in reactor head of exploitation; this protective agent can make Fe, Ca organic compound be diffused into the protective agent granule interior rapidly on the one hand and remove and be deposited in the catalyst duct; on the other hand; to the particle in the feedstock oil, can play interception, catch with filtration and the particle that will tackle equally, catch and filter and be deposited in the catalyst duct.

Chinese patent ZL98111379.6 has disclosed a kind of hydrogenation protecting catalyst and preparation method thereof, and catalyst carrier is a ultra-large aperture, and the aperture is the bimodal hole of 0.1～30 μ m, and the catalyst pore volume is 0.1～0.8ml/g, specific surface 0.1～20m²/ g contains group vib metallic element 6.65m%～20.0m% and/or the metallic element 8.71m%～26.13m% of VIII family.The preparation method adopts particle to pile up legal system to be equipped with alumina support, adopts platiniferous solution and solution containing nickel equivalent impregnation then, and the catalyst behind the dipping is at 100～120 ℃ of drying 2～5h, at 500～550 ℃ of following roasting 2～5h.Its key is that the preparation method of carrier is that particle is piled up method, the preparation method of carrier is as follows: at first with the aluminium oxide extruded moulding, spherical or the strip aluminium oxide of gained is 100～200 ℃ of oven dry, with the spherical or strip aluminium oxide of oven dry pulverize after getting through 60～120 purposes sieve the aluminium oxide of fine granularity, the pre-calcination 4～8h of the aluminium oxide of fine granularity, obtain having the aluminium oxide of certain micropore and pore volume, choose the aluminium oxide of certain particle size, alumina particle is piled up bonding, whole behind the extruded moulding for spherical, make alumina support behind calcination 3～6h.

Chinese patent ZL97121095.0 has disclosed a kind of catalyst for heavy oil hydrogenation demetal and preparation method thereof.Catalyst carrier is cellular or the sinter of Raschig ring shape alkali metal containing mineral and inertia aluminium oxide, and active component is group vib metallic element and/or VIII family metallic element and P auxiliary agent.This catalyst pore volume is 0.01-0.4ml/g, and specific area is 2.0-20.0m²/ g.Concrete preparation method is as follows: with inertia aluminium oxide, alkali metal mineral, binding agent, expanding agent batch mixing spin or extrusion modling, carrier is made in drying, roasting again, supports the hydrogenation activity component then.Binding agent is divided into solid phase binder and liquid adhesive.Solid phase binder comprises clay, talcum powder, kaolin, and liquid adhesive comprises waterglass or dextrine powder or nitric acid.The carrier total amount is made up of alkali metal mineral, inertia aluminium oxide, binding agent, and surplus is the amount of binding agent except that alkali metal mineral, inertia aluminium oxide, is about 5-20w%.Expanding agent is the material that carbon powder, wood chip, field can be burnt after for roastings such as powder, methylcellulose, and for roller forming technology, its granularity is the 20-40 order, and for extrusion forming process, its granularity is＜180 orders, and consumption is the 5-25w% of vehicle weight.The temperature that inertia aluminium oxide, alkali metal mineral etc. are made the roasting of carrier is 1050-1200 ℃.

The open CN1583271A (application number 200410041065.7) of Chinese patent has disclosed a kind of porous ceramics catalyst carrier, it is improvement to alumina oxide matrix porous ceramic catalyst carrier, employing is by the fine powder of 85-96wt% based on alpha-aluminium oxide, the calcium oxide of 3-12wt% (in CaO) fine powder, the rare earth oxide lanthanum of 5wt% and/or iridium are formed (all percentage number averages are benchmark with the carrier final weight).This invention thinks and has formed structural opening micropore (because field difference, so the micropore here refers to μ m level hole) micropore size evenly by reaction that the mechanical strength height can obtain the catalyst carrier of intensity greater than 25ON/cm, specific area and intensity height.The micropore that forms not only high temperature sintering also is difficult for porcelainization, and pore structure is stable, helps infiltrating catalyst and fully participates in reaction; And making gained catalyst carrier water pore volume height, water pore volume can support more catalyst greater than 25%.Therefore catalyst carrier of the present invention, catalyst-loaded after, have catalytic reaction rate height, catalyst-loadedly substantially all can participate in catalytic reaction.

U.S. Pat 5217603 has disclosed a kind of technology of utilizing the porous inorganic oxide particle to carry out hydrotreatment, the about 1m of the specific surface of this oxide²About/g, pore volume is 0.1ml/g at least, bore dia at least 10 μ m.This oxide comprises aluminium oxide, silica, silica-alumina, silica-magnesia, magnesia, titanium oxide etc.But do not relate to the preparation of this kind oxide in the patent.

U.S. Pat 5266548 has disclosed a kind of carrier based on aluminium oxide, and pore volume is between 0.2-0.6cm³/ g, specific surface is between 0.2-10m²/ g, average pore size is between 0.1-100 μ m.The preparation method is as follows: with the Alpha-alumina and the raw material that can burn and binding agent mixed extrusion molding of granular size between 0.2-20 μ m, after required carrier is made in roasting.Being used to of adding provides the raw material of burning in the hole of 0.1-100 μ m to comprise material such as rosin, sawdust and the shell etc. of coke, powdered carbon, graphite, graininess plastics and formation naturally.

The carrier that can obtain to have super big hole by above-mentioned prior art, but these super big hole are isolated mutually each other causes it to catch or filter the poor performance of metal impurities in the feedstock oil or particle.

Summary of the invention

The technical problem to be solved in the present invention is to lack filling at existing in prior technology, provides a kind of new preparation to have millimeter method of level macropore hydrogenation activity protecting agent and the hydrogenation activity protective agent that is prepared by this method.

The invention provides a kind of preparation method of hydrogenation protecting agent; comprise the precursor of the heat-resistant inorganic oxide of the heat-resistant inorganic oxide of one or more porous and/or porous is mixed with at least a organic matter; moulding; dry also roasting; described baking temperature is 60～300 ℃; 2～15 hours drying times; sintering temperature is 500～1200 ℃; roasting time is 1-10 hour; the mixed proportion of the heat-resistant inorganic oxide of described organic matter and described porous is 0.5～20: 80～99.5; wherein, described organic compound is that fusing point is between 30～200 ℃; 0.3～2.5 millimeter of particle diameter and water-insoluble solid particle.

The invention provides a kind of hydrogenation protecting agent; the heat-resistant inorganic oxide that contains one or more porous; it is characterized in that; the total pore volume of described protective agent is 0.3-1.5 millimeter/gram; wherein contain millimeter level macropore; millimeter level macropore bore dia is 0.1～1.5 micron, and millimeter level macropore pore volume is 0.05～0.7 a milliliter/gram, the method preparation that described catalyst is provided by the invention described above.

Compared with prior art, organic expanding agent that the inventive method is introduced, it is a kind of organic matter that can form millimeter level (0.1～1.5 millimeter) macropore, this organic matter melts in dry run, and make the millimeter level organic matter in the article shaped in article shaped, redistribute, also keep the millimeter level macropore that has formed by millimeter level organic particle simultaneously.Hydrogenation protecting agent provided by the invention, the pore distribution curve that its mercury injection method analysis obtains two peaks occur at 4～30 microns and 0.1～1.5 millimeter respectively, form bimodal distribution.Protective agent with this pore structure is when the high feedstock oil of hydrotreatment particle content height, Fe and/or Ca content, and tool has great advantage.When for example handling the residual oil of Fe content 50 μ g/g, Ca content 25 μ g/g; under same operating condition; conventional protective agent and protective agent of the present invention operation are after 3 months; utilize electron probing analysis to show; wherein Fe and Ca mainly are distributed in outer surface (formation shell) on protective agent; this distribution not only makes the protective agent utilization rate obviously reduce, and makes protective agent hold amount of metal simultaneously and obviously reduces, thereby protectant function is reduced.And the hydrogenation protecting agent provided by the invention of turning round under identical condition utilizes electron probing analysis to show, wherein Fe is relative even with the radial distribution of Ca on protective agent of the present invention, obviously is different from the GPF (General Protection False agent.Therefore, protective agent of the present invention can hold more metal impurities or particle, has obviously good protective agent function.

Description of drawings

Fig. 1 is the pore distribution curve that the mercury injection method of hydrogenation protecting agent provided by the invention is analyzed.

Hydrogenation protecting agent Fe and Ca distribution curve in the hydrogenation protecting agent after estimating 3 months on the medium-sized evaluating apparatus that Fig. 2 a provides for prior art.

Fig. 2 b is hydrogenation protecting agent provided by the invention Fe and Ca distribution curve in the hydrogenation protecting agent after estimating 3 months on the medium-sized evaluating apparatus.

The specific embodiment

According to method provided by the invention, wherein said baking temperature is preferably 80～200 ℃, is preferably 4～10 hours drying time, and sintering temperature is preferably 550～1000 ℃, and more preferably 600～900 ℃, roasting time is preferably 1-6 hour.

Described organic matter is preferably one or more in paraffin, ceresine, microwax, polyethylene or the polypropylene, the mixed proportion of the precursor of the heat-resistant inorganic oxide of described organic matter and described porous and/or the heat-resistant inorganic oxide of porous is preferably 1～15: 85～99, more preferably 2～12: 88～98, the particle diameter of described organic compound is preferably 0.5～1.8 millimeter, more preferably 0.8～1.5 millimeter.

The heat-resistant inorganic oxide precursor of the heat-resistant inorganic oxide of described porous and/or porous is selected from the heat-resistant inorganic oxide of various Chang Zuowei host materials and in the precursor one or more thereof.For example, the optional self-alumina of described heat-resistant inorganic oxide, silica, titanium oxide, magnesia, aluminium oxide-magnesia, silica-alumina, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, silica-zirconia, the oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolite, in the clay one or more, preferred aluminium oxide, silica, in silica-alumina and the precursor thereof one or more, further preferred aluminium oxide and precursor thereof.

Described moulding can be carried out according to a conventional method, as methods such as compressing tablet, spin, extrusion moldings.For example when extrusion molding, described mixture can be mixed and add an amount of extrusion aid and/or peptizing agent, extrusion molding then with an amount of water.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not give unnecessary details at this.

According to method provided by the invention, also be included in and introduce at least a step that is selected from IA and IIA family metal component in the described protective agent.In preferred embodiment, the described introducing method that is selected from IA and IIA family metal component is when the precursor of the heat-resistant inorganic oxide of the heat-resistant inorganic oxide of one or more porous and/or porous is mixed with at least a organic matter, introduce at least a IA and the IIA family metal component of being selected from, moulding afterwards, dry and roasting.In oxide and with described protective agent is benchmark, and the introducing amount of described metal component makes the content of metal part described in the final protective agent be not more than 5 weight %, is preferably 0.5～3 weight %.Described IA and IIA family metal component are preferably one or more in lithium, sodium, potassium, magnesium, the calcium.

Catalyst provided by the invention is suitable as hydrogenation protecting catalyst, is used for the process that heavier hydrocarbon feeds is carried out.Described heavier hydrocarbon feeds comprises crude oil, normal pressure or decompression residuum and normal pressure or vacuum distillate.

Following example will the present invention will be further described.

Agents useful for same in the example except that specifying, is chemically pure reagent.

Example 1～4 explanation the inventive method and catalyst thereof.

Example 1

Get boehmite (the abbreviation SD powder that Shandong Aluminium Industry Co., Ltd produces; butt 73%) 100 grams, (granular size is between 0.5～1.5 millimeter for Witcodur 272 10 gram; 65 ℃ of fusing points), the sesbania powder 3 as extrusion aid restrains; above-mentioned material is mixed 5 minutes; adding is 40 milliliters of the salpeter solutions of 5.6 weight % as the concentration of peptizing agent; on banded extruder, mix and pinched 10 minutes; extruded moulding then; article shaped is the cylinder bar shaped of 5 millimeters of external diameters; following dry 6 hours in 120 ℃ afterwards; 800 ℃ of following roastings 3 hours obtain final protective agent R-1.Through pressing the mercury analysis, total pore volume of R-1 is 0.45 a milliliter/gram, and wherein millimeter level macropore is between 0.3～1.5 millimeter, and its pore volume is 0.21 a milliliter/gram.Fig. 1 is seen in the pore size distribution of R-1.

Example 2

The boehmite (with example 1) 100 of getting Shandong Aluminium Industry Co., Ltd's production restrains, (granular size is between 1～2 millimeter for low density polyethylene (LDPE) 11 grams; 120 ℃ of fusing points), potassium nitrate 3 gram, as sesbania powder 3 grams of extrusion aid; above-mentioned material is mixed 5 minutes; adding is 40 milliliters of the salpeter solutions of 5.6 weight % as the concentration of peptizing agent; on banded extruder, mix and pinched 10 minutes; extruded moulding then; article shaped is the cylinder bar shaped of 5 millimeters of external diameters; following dry 8 hours in 180 ℃ afterwards; 950 ℃ of following roastings 2 hours obtain final protective agent R-2.Through pressing the mercury analysis, total pore volume of R-2 is 0.4 a milliliter/gram, and wherein millimeter level macropore is between 0.8～1.8 millimeter, and its pore volume is 0.23 a milliliter/gram.

Example 3

Get macropore boehmite (the abbreviation CL powder that Chang Ling refinery company catalyst plant is produced; butt 67%) 100 grams; (granular size is between 0.8～1.5 millimeter for paraffin 7 grams; 60 ℃ of fusing points); lithium nitrate 1.5 grams; sesbania powder 3 grams as extrusion aid; above-mentioned material is mixed 5 minutes; adding is 115 milliliters of the salpeter solutions of 2.2 weight % as the concentration of peptizing agent; on banded extruder, mix and pinched 10 minutes; extruded moulding then; article shaped is the cylinder bar shaped of 5 millimeters of external diameters; be shaped as the spheroid shape of 5～7 millimeters of external diameters through trimmer; afterwards in 150 ℃ dry 4 hours down, 700 ℃ of following roastings 5 hours obtain final protective agent R-3.Through pressing the mercury analysis, total pore volume of R-3 is 1.15 a milliliters/gram, and wherein millimeter level macropore is between 0.5～1.5 millimeter, and its pore volume is 0.15 a milliliter/gram.

Example 4

Get macropore boehmite (with example 3) 100 grams that Chang Ling refinery company catalyst plant is produced; (granular size is between 0.8～1.5 millimeter for low-density polypropylene 4 grams; 160 ℃ of fusing points); magnesium nitrate 5 grams; sesbania powder 3 grams as extrusion aid; above-mentioned material is mixed 5 minutes; adding is 115 milliliters of the salpeter solutions of 2.2 weight % as the concentration of peptizing agent; on banded extruder, mix and pinched 10 minutes; extruded moulding then; article shaped is 10 millimeters of external diameters; the Raschig ring that internal diameter is 4 millimeters; following dry 5 hours in 200 ℃ afterwards; 600 ℃ of following roastings 6 hours obtain final protective agent R-4.Through pressing the mercury analysis, total pore volume of R-4 is 1.2 a milliliters/gram, and wherein millimeter level macropore is between 0.5～1.5 millimeter, and its pore volume is 0.13 a milliliter/gram.

Comparative Examples 1

CL powder 100 grams, the granular size of getting the catalyst plant production of Chang Ling refinery company mix 5 minutes between 0.8-1.5 millimeter carbon black 10 grams, sesbania powder 3 grams and magnesium nitrate 5.0 grams; add concentration and be 115 milliliters of the dilute nitric acid solutions of 2.2w%; mix and pinched 10 minutes; extruded moulding then; article shaped is the Raschig ring of 10 millimeters of external diameters, 4 millimeters of internal diameters; afterwards in 150 ℃ dry 5 hours down, 600 ℃ of following roastings after 6 hours particle burst seriously, do not have the protective agent of complete Raschig ring shape basically.

5～6 example explanations of example the invention provides hydrogenation protecting agent performance.

Example 5

Estimate protective agent R-1 respectively on 200 milliliters medium-sized evaluating apparatus, raw materials used oil is decompression residuum, and wherein Fe content is that 50 μ g/g, Ca content are 25 μ g/g.Appreciation condition is 385 ℃ of reaction temperatures, hydrogen dividing potential drop 13MPa, volume space velocity 0.6h^-1, hydrogen to oil volume ratio 600.Estimate after 3 months and stop work, the protective agent after estimating is cooked electron probe and carbon deposit analysis, Fe on the R-1 and Ca distribute and see that Fig. 3 b, the total deposition of Fe and Ca are 16.84 weight %, and coke content is 15.2 weight %.

Example 6

According to example 5 identical condition evaluating hydrogenation protecting agent R-2, the protective agent after the evaluation is cooked electron probe and carbon deposit analysis, the Fe on the R-2 and Ca distribute similar with R-1, see Fig. 3 b, the total deposition of Fe and Ca is 17.82 weight %, coke content is 12.5 weight %.

Comparative Examples 2

According to the identical condition evaluatings industry of example 5 hydrogenation protecting agent W (Chang Ling refinery company catalyst plant product); protective agent after the evaluation is cooked electron probe and carbon deposit analysis; Fe on the W and Ca distribute and see that Fig. 3 a, the total deposition of Fe and Ca are 13.24 weight %, and coke content is 17.4 weight %.

Above-mentioned evaluation result can show, compares with the catalyst that prior art provides, and Fe and Ca metal are more even in the radial distribution of the catalyst deposit that the inventive method provides, and the invention provides catalyst utilization and holds the metal ability and obviously improve thereby make.In addition, introduce alkali metal and/or alkaline-earth metal in hydrogenation protecting agent provided by the invention, the catalyst anti-carbon deposition ability improves, and is favourable to the performance of further raising hydrogenation protecting agent.

Claims (12)

Translated fromChinese

1、一种加氢保护剂的制备方法，包括将一种或几种多孔的耐热无机氧化物和/或多孔的耐热无机氧化物的前身物与至少一种有机物混合、成型、干燥并焙烧，所述干燥温度为60～300℃，干燥时间2～15小时，焙烧温度为500～1200℃，焙烧时间为1-10小时，所述有机物与所述多孔的耐热无机氧化物的混合比例为0.5～20∶80～99.5，其中，所述有机物为熔点介于30～200℃、粒径0.3～2.5毫米且不溶于水的固体颗粒。1. A method for preparing a hydrogenation protecting agent, comprising mixing one or more porous heat-resistant inorganic oxides and/or precursors of porous heat-resistant inorganic oxides with at least one organic substance, molding, drying and Calcination, the drying temperature is 60-300°C, the drying time is 2-15 hours, the calcination temperature is 500-1200°C, the calcination time is 1-10 hours, the mixture of the organic matter and the porous heat-resistant inorganic oxide The ratio is 0.5-20:80-99.5, wherein the organic matter is a water-insoluble solid particle with a melting point between 30-200° C. and a particle size of 0.3-2.5 mm.2、根据权利要求1所述的方法，其特征在于，所述干燥温度为80～200℃，干燥时间4～10小时，焙烧温度为550～1000℃，焙烧时间为1-6小时。2. The method according to claim 1, characterized in that the drying temperature is 80-200°C, the drying time is 4-10 hours, the calcination temperature is 550-1000°C, and the calcination time is 1-6 hours.3、根据权利要求2所述的方法，其特征在于，所述焙烧温度为600～900℃。3. The method according to claim 2, characterized in that the calcination temperature is 600-900°C.4、根据权利要求1所述的方法，其特征在于，所述有机物选自石蜡、地蜡、微晶蜡、聚乙烯或聚丙烯中的一种或几种，所述有机物与所述多孔的耐热无机氧化物和/或多孔的耐热无机氧化物的前身物的混合比例为1～15∶85～99，所述有机物的粒径为0.5～1.8毫米。4. The method according to claim 1, characterized in that, the organic matter is selected from one or more of paraffin wax, ozokerite, microcrystalline wax, polyethylene or polypropylene, and the organic matter and the porous The mixing ratio of the heat-resistant inorganic oxide and/or the precursor of the porous heat-resistant inorganic oxide is 1-15:85-99, and the particle size of the organic matter is 0.5-1.8 mm.5、根据权利要求4所述的方法，其特征在于，所述有机物与所述多孔的耐热无机氧化物和/或多孔的耐热无机氧化物的前身物的混合比例为2～12∶88～98，所述有机物的粒径为0.8～1.5毫米。5. The method according to claim 4, characterized in that the mixing ratio of the organic matter to the porous heat-resistant inorganic oxide and/or the precursor of the porous heat-resistant inorganic oxide is 2 to 12:88 ~98, the particle size of the organic matter is 0.8-1.5 mm.6、根据权利要求1所述的方法，其特征在于，所述方法还包括在将一种或几种多孔的耐热无机氧化物和/或多孔的耐热无机氧化物的前身物与至少一种有机物混合时，引入至少一种选自第IA和IIA族金属组分，以氧化物计并以所述保护剂为基准，所述金属组分的引入量使最终保护剂中所述金属组分的含量不大于5重量％。6. The method according to claim 1, characterized in that the method further comprises combining one or more porous heat-resistant inorganic oxides and/or precursors of porous heat-resistant inorganic oxides with at least one When the two organic substances are mixed, introduce at least one metal component selected from group IA and IIA, in terms of oxides and based on the protective agent, the introduction amount of the metal component is such that the metal group in the final protective agent The content of the component is not more than 5% by weight.7、根据权利要求6所述的方法，其特征在于，所述第IA和IIA族金属组分为选自锂、钠、钾、镁、钙的一种或几种，以氧化物计并以所述保护剂为基准，所述金属组分的引入量使最终保护剂中所述金属组分的含量为0.5～3重量％。7. The method according to claim 6, characterized in that, the group IA and IIA metal components are one or more selected from lithium, sodium, potassium, magnesium, calcium, calculated as oxides and expressed as The protecting agent is used as a reference, and the introduction amount of the metal component is such that the content of the metal component in the final protecting agent is 0.5-3% by weight.8、一种加氢保护剂，含有一种或几种多孔的耐热无机氧化物，其特征在于，所述保护剂总的孔容为0.3-1.5毫升/克，其中含有毫米级大孔，毫米级大孔孔直径为0.1～1.5毫米，毫米级大孔孔容为0.05～0.7毫升/克，所述保护剂由权利要求1～7所述的任意一种方法制备。8. A hydrogenation protective agent, containing one or more porous heat-resistant inorganic oxides, characterized in that the total pore volume of the protective agent is 0.3-1.5 ml/g, which contains millimeter-sized macropores, The diameter of the millimeter-scale macropores is 0.1-1.5 mm, the volume of the millimeter-scale macropores is 0.05-0.7 ml/g, and the protective agent is prepared by any one of the methods described in claims 1-7.9、根据权利要求8所述的保护剂，其特征在于，所述毫米级大孔孔直径为0.3～1毫米，毫米级大孔孔容为0.1～0.5毫升/克。9. The protective agent according to claim 8, characterized in that the diameter of the millimeter-scale macropores is 0.3-1 mm, and the volume of the millimeter-scale macropores is 0.1-0.5 ml/g.10、根据权利要求9所述的保护剂，其特征在于，所述毫米级大孔孔容为0.1～0.35毫升/克。10. The protective agent according to claim 9, characterized in that the pore volume of the millimeter-sized macropores is 0.1-0.35 ml/g.11、根据权利要求8所述的保护剂，其特征在于，所述保护剂还含有至少一种选自第IA和IIA族金属组分，以氧化物计并以所述保护剂为基准，所述金属组分的含量不大于5重量％。11. The protective agent according to claim 8, characterized in that, the protective agent also contains at least one metal component selected from group IA and IIA, calculated as oxides and based on the protective agent, so The content of the metal component is not more than 5% by weight.12、根据权利要求11所述的保护剂，其特征在于，所述第IA和IIA族金属组分选自锂、钠、钾、镁、钙的一种或几种，以氧化物计并以所述保护剂为基准，所述金属组分的含量为0.5～3重量％。12. The protective agent according to claim 11, characterized in that, the group IA and IIA metal components are selected from one or more of lithium, sodium, potassium, magnesium, calcium, calculated as oxides and expressed as The protective agent is used as a basis, and the content of the metal component is 0.5-3% by weight.

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