阅读说明：本技术 催化剂载体及其制备方法和加氢催化剂以及加氢裂化方法 (Catalyst carrier, preparation method thereof, hydrogenation catalyst and hydrocracking method ) 是由 董松涛 聂红 杨平 赵阳 赵广乐 于 2019-10-31 设计创作，主要内容包括：本发明涉及载体制备领域,公开了一种催化剂载体,该载体含有耐热无机氧化物和分子筛中的至少一种；该载体的吸水率与BET孔容的差值R不低于0.2mL/g。催化剂载体的制备方法包括：(1)将载体前驱体、发泡剂、水以及可选的助挤剂、可选的粘合剂混合得到的混合物进行混捏、成型；(2)将步骤(1)得到的成型物进行焙烧。由本发明提供的载体制备的加氢催化剂在用于烃油的加氢裂化时,在获得较高的航煤收率的同时,还能够获得高的催化活性。(The invention relates to the field of carrier preparation, and discloses a catalyst carrier, which contains at least one of heat-resistant inorganic oxide and molecular sieve; the difference R between the water absorption of the carrier and the BET pore volume is not less than 0.2 mL/g. The preparation method of the catalyst carrier comprises the following steps: (1) mixing a carrier precursor, a foaming agent, water, an optional extrusion aid and an optional adhesive to obtain a mixture, kneading and molding; (2) and (2) roasting the formed product obtained in the step (1). When the hydrogenation catalyst prepared by the carrier provided by the invention is used for hydrocracking of hydrocarbon oil, high aviation kerosene yield can be obtained, and high catalytic activity can be obtained.)

1. A catalyst support comprising at least one of a refractory inorganic oxide and a molecular sieve; the difference R between the water absorption of the carrier and the BET pore volume is not less than 0.2 mL/g.

2. The carrier according to claim 1, wherein the difference R between the water absorption of the carrier and the BET pore volume is between 0.2 and 0.8mL/g, preferably between 0.2 and 0.5 mL/g.

3. The carrier according to claim 1, wherein the ratio of the difference R between the water absorption of the carrier and the BET pore volume to the water absorption of the carrier is 10-50%, preferably 15-40%;

preferably, the carrier is spherical and/or strip-shaped, preferably strip-shaped, and further preferably multilobal strip-shaped;

preferably, the equivalent diameter of the support is not more than 5mm, preferably not more than 3mm, more preferably not more than 2mm, still more preferably 0.8-2 mm.

4. The carrier according to claim 1, wherein the carrier has a radial crush strength of 14-30N/mm, preferably 18-26N/mm;

preferably, the bulk ratio of the carrier is 0.35 to 0.55g/mL, more preferably 0.40 to 050 g/mL.

5. The carrier according to any one of claims 1 to 4, wherein the heat-resistant inorganic oxide is at least one selected from the group consisting of alumina, silica, titania, magnesia, zirconia, thoria and beryllia, preferably at least one of alumina, silica, titania and zirconia;

preferably, the molecular sieve is selected from at least one of ten-membered ring silicoaluminophosphate molecular sieves, twelve-membered ring silicoaluminophosphate molecular sieves, fourteen-membered ring silicoaluminophosphate molecular sieves and eighteen-membered ring silicoaluminophosphate molecular sieves;

preferably, the molecular sieve is selected from at least one of ZRP molecular sieve, Y molecular sieve, beta molecular sieve, mordenite, ZSM-5 molecular sieve, MCM-41 molecular sieve, omega molecular sieve, ZSM-12 molecular sieve and MCM-22 molecular sieve, and is further preferably at least one of Y molecular sieve, beta molecular sieve, ZSM-5 molecular sieve and mordenite;

preferably, the content of the heat-resistant inorganic oxide is 1 to 99% by weight, more preferably 70 to 99% by weight, based on the total amount of the carrier; the content of the molecular sieve is 1 to 99% by weight, more preferably 1 to 30% by weight.

6. A method of preparing a catalyst support, the method comprising:

(1) mixing a carrier precursor, a foaming agent, water, an optional extrusion aid and an optional adhesive to obtain a mixture, kneading and molding;

(2) and (2) roasting the formed product obtained in the step (1).

7. The method for preparing according to claim 6, wherein the foaming agent is an animal protein foaming agent and/or a plant foaming agent, preferably an animal protein foaming agent;

preferably, the animal protein foaming agent is selected from at least one of an animal hoof and horn foaming agent, an animal hair foaming agent and an animal blood gel foaming agent;

preferably, the blowing agent is introduced in the form of a solution.

8. The production method according to claim 6, wherein the support precursor is selected from at least one of a refractory inorganic oxide, a refractory inorganic oxide precursor, and a molecular sieve;

preferably, the heat-resistant inorganic oxide is selected from at least one of alumina, silica, titania, magnesia, zirconia, thoria and beryllia, preferably at least one of alumina, silica, titania and zirconia;

preferably, the molecular sieve is selected from at least one of ten-membered ring silicoaluminophosphate molecular sieves, twelve-membered ring silicoaluminophosphate molecular sieves, fourteen-membered ring silicoaluminophosphate molecular sieves and eighteen-membered ring silicoaluminophosphate molecular sieves;

preferably, the molecular sieve is selected from at least one of ZRP molecular sieve, Y molecular sieve, beta molecular sieve, mordenite, ZSM-5 molecular sieve, MCM-41 molecular sieve, omega molecular sieve, ZSM-12 molecular sieve and MCM-22 molecular sieve, and is further preferably at least one of Y molecular sieve, beta molecular sieve, ZSM-5 molecular sieve and mordenite;

preferably, the refractory inorganic oxide and/or precursor of the refractory inorganic oxide and the molecular sieve are used in amounts such that the refractory inorganic oxide is contained in the carrier obtained in an amount of 1 to 99% by weight, more preferably 70 to 99% by weight, based on the total amount of the carrier; the content of the molecular sieve is 1 to 99% by weight, more preferably 1 to 30% by weight.

9. The production method according to claim 6, wherein the extrusion aid is selected from at least one of sesbania powder, cellulose and derivatives thereof, starch and derivatives thereof, ethylene glycol and diethylene glycol;

the adhesive is selected from at least one of hydroxymethyl cellulose, inorganic acid, starch and derivatives thereof, silica sol and aluminum sol.

10. The production method according to claim 6, wherein the mixing of step (1) includes: mixing the carrier precursor and the extrusion aid, and then adding the foaming agent, the adhesive and the water to obtain the mixture.

11. The production method according to any one of claims 6 to 10,

the amount of the foaming agent is 0.5-20mL, preferably 1.0-10mL, relative to 100g of the carrier precursor on a dry basis;

the amount of the extrusion aid is 0.1-6g relative to 100g of the carrier precursor on a dry basis;

the binder is used in an amount of 0.1 to 10g, relative to 100g of the carrier precursor on a dry basis.

12. The production method according to any one of claims 6 to 11, wherein the shaped product is spherical and/or strip-shaped, preferably strip-shaped, and more preferably multi-lobal strip-shaped;

preferably, the equivalent diameter of the molding is not more than 5mm, preferably not more than 3mm, more preferably not more than 2mm, and still more preferably 0.8 to 2 mm;

preferably, the conditions of the calcination include: the temperature is 350-700 ℃, preferably 450-650 ℃; the time is 1 to 10 hours, preferably 2 to 6 hours.

13. A catalyst support obtainable by the process of any one of claims 6 to 12.

14. A hydrogenation catalyst comprising the carrier of any one of claims 1 to 4 and 13 and a group VIB metal element and a group VIII metal element supported on the carrier;

preferably, the content of the VIB group metal element is 10-40 wt%, the content of the VIII group metal element is 2-10 wt%, and the content of the carrier is 50-88 wt%, calculated by oxides, based on the total amount of the catalyst.

15. A hydrocracking process, comprising: the method comprises the following steps: contacting a hydrocarbon oil with a hydrocracking catalyst under hydrocracking conditions, wherein the hydrocracking catalyst is the hydrocracking catalyst of claim 14.

Technical Field

The invention relates to the field of carrier preparation, in particular to a catalyst carrier and a preparation method thereof, a hydrogenation catalyst and a hydrocracking method.

Background

The catalyst carrier is also called a support (support) and is one of the compositions of the supported catalyst. The catalytically active components are supported on the surface of a carrier, which is mainly used to support the active components and to give the catalyst specific physical properties, whereas the carrier itself generally does not have catalytic activity. Most supports are products in the catalyst industry, and commonly used are alumina supports, silica gel supports, activated carbon supports, and certain natural products such as pumice, diatomaceous earth, and the like.

The support enables the catalyst to be produced with suitable shape, dimensions and mechanical strength to meet the operating requirements of an industrial reactor; the carrier can disperse the active components on the surface of the carrier, so that higher specific surface area is obtained, and the catalytic efficiency of the active components per unit mass is improved. Such as platinum on activated carbon. If molecular sieve is used as carrier, the platinum can reach the dispersity close to atomic level. The carrier can also prevent the active component from sintering in the using process, and improve the heat resistance of the catalyst. For some strongly exothermic reactions, the support dilutes the active components in the catalyst to meet the heat balance requirements; carriers of good thermal conductivity, such as metals, silicon carbide, etc., help to remove the heat of reaction and avoid local overheating of the catalyst surface. The carrier can also be solid catalyst prepared by loading some catalyst originally used in homogeneous reaction on solid carrier, such as solid acid catalyst prepared by adsorbing phosphoric acid in diatomite, and immobilized enzyme prepared by loading enzyme on carrier.

The geometric shape and the geometric dimension of the catalyst have influence on fluid resistance, air flow velocity, bed temperature gradient distribution, concentration gradient distribution and the like, and are also related to the effective utilization rate of active metal of the catalyst, the carrying of reaction heat in the reaction process and the like. In order to fully exploit the potential of the catalyst, the optimum shape and size should be chosen, which requires the use of the most suitable support shaping and preparation method.

The selection of the geometry and dimensions of a commercial catalyst often requires balancing in several ways while simultaneously taking into account several properties of the catalyst. To achieve different goals, catalysts of a wide variety of morphologies are currently being developed. Usually in the form of spheres, which are commonly used for fluidized catalysts, or catalysts for which the flowability is particularly critical. The strip-shaped and fixed bed catalyst is further developed into a cylindrical strip, a trilobal strip, a quadralobe strip, other multilobal strips and deformed multilobal strips on the basis of the strip-shaped catalyst. Barrel-shaped strips, i.e. strips with holes in the cylinder, such as typical raschig rings, cross rings, pall rings, step rings, etc. Honeycomb supports, i.e., a matrix of cordierite or alumina on which regularly arranged channels are commonly used for SCR and automotive exhaust treatment, etc.

In order to improve the catalyst diffusion performance, the amount of macropores or super-macropores is increased by adding a forming aid.

Chinese patent CN1115388C proposes a hydrogenation protective agent and a preparation method thereof, which adopts carbon black or an organic pore-enlarging agent as a pore-enlarging additive, and is said to have higher catalyst activity, lower carbon deposition amount, better activity stability and higher strength.

Chinese patent CN103418441B discloses a hydrorefining catalyst, the carrier of which is a molding containing carbon, cellulose ether and hydrated alumina. The disclosed hydrorefining catalyst has excellent hydrorefining performance of hydrocarbon oil, and meanwhile, the preparation method is simple and the production cost is low.

Chinese patent CN101890382B proposes a method for preparing a catalyst, which comprises rod-like nano-oxide in addition to alumina material. The catalyst prepared by the method disclosed by the invention has large pore volume, large pore diameter and good pore canal penetrability, and is particularly suitable for residue fixed bed hydrogenation.

Chinese patent CN102015101B proposes a porous body precursor, a shaped porous body, their preparation methods and end products based on them, and proposes a method for preparing a catalyst and a carrier by using a plurality of alumina precursors with different properties, and improves the pore structure by a mixed way.

The pore channel modifier adopted in the prior art is mainly used for occupying space and forming pores based on fillers, or is added with an auxiliary agent, or adopts water and an alumina precursor with different properties, and realizes the optimization of pore channels by improving the connection mode between basic units. The common characteristics of the two methods are that the amount of the needed auxiliary agent is large, and in addition, the obtained pore channel has smaller general pore diameter.

Disclosure of Invention

The present invention aims to overcome the above problems in the prior art and provide a catalyst carrier, a preparation method thereof, a hydrogenation catalyst and a hydrocracking method. The preparation method of the catalyst carrier improves the pore structure of the catalyst or the carrier by using lower cost, strengthens the diffusion process of macromolecules, and improves the activity of the catalyst and the accessibility of an active center. When the hydrogenation catalyst prepared by the carrier provided by the invention is used for hydrocracking of hydrocarbon oil, high catalytic activity can be obtained while high yield of medium aviation kerosene is obtained.

In order to achieve the above object, the first aspect of the present invention provides a catalyst carrier comprising at least one of a refractory inorganic oxide and a molecular sieve; the difference R between the water absorption of the carrier and the BET pore volume is not less than 0.2 mL/g.

Preferably, the carrier has a radial crushing strength of 14 to 30N/mm, more preferably 18 to 26N/mm.

In a second aspect, the present invention provides a method for preparing a catalyst carrier, the method comprising:

(1) mixing a carrier precursor, a foaming agent, water, an optional extrusion aid and an optional adhesive to obtain a mixture, kneading and molding;

(2) and (2) roasting the formed product obtained in the step (1).

Preferably, the foaming agent is an animal protein foaming agent.

In a third aspect, the present invention provides a catalyst support obtained by the above-mentioned production method.

The fourth aspect of the invention provides a hydrogenation catalyst, which comprises the carrier, and a VIB group metal element and a VIII group metal element loaded on the carrier.

In a fifth aspect, the present invention provides a hydrocracking method, which includes contacting a hydrocarbon oil with a hydrocracking catalyst under hydrocracking conditions, where the hydrocracking catalyst is the hydrocracking catalyst provided by the present invention.

According to the preparation method of the catalyst carrier, the foaming agent is added in the forming process, and the gas component can be wrapped in the forming body due to the addition of the foaming agent, so that the proportion of macropores and super-macropores in the carrier in the whole pore volume is improved, and the smoothness of the pore channel of the carrier is improved. The catalyst prepared by the carrier provided by the invention can effectively improve the activity of the catalyst and the accessibility of an active center, is very suitable for the diffusion of macromolecules, and can obtain high aviation kerosene yield and high catalytic activity when being used for hydrocracking of hydrocarbon oil.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention, there is provided a catalyst support comprising at least one of a refractory inorganic oxide and a molecular sieve; the difference R between the water absorption of the carrier and the BET pore volume is not less than 0.2 mL/g.

In the invention, the water absorption is wiping water absorption. The dry wiping water absorption rate of the carrier is that the dry carrier is soaked in deionized water for more than 30 minutes at room temperature (20-25 ℃), and is wiped by using filter paper after filtration to obtain the mass of the carrier after water absorption, and the ratio of the mass difference between the mass of the carrier without water absorption and the mass of the carrier without water absorption is the dry wiping water absorption rate.

According to one embodiment of the invention, the dry water absorption of the catalyst support is 0.8 to 2mL/g, preferably 0.9 to 1.5 mL/g.

According to one embodiment of the invention, the BET pore volume of the catalyst support is between 0.62 and 1mL/g, preferably between 0.65 and 0.9 mL/g.

In the present invention, the BET pore volume is measured by the method specified in RIPP 151-90, unless otherwise specified.

According to the present invention, the difference R between the water absorption of the carrier and the BET pore volume is preferably 0.2 to 0.8mL/g, more preferably 0.2 to 0.5 mL/g.

According to the invention, the support preferably has a radial crushing strength of 14 to 30N/mm, preferably 18 to 26N/mm. In the present invention, the radial crushing strength of the catalyst carrier was measured on a crushing strength measuring apparatus of QCY-602 type (manufactured by soda research, chemical engineering Co., Ltd.) according to the method prescribed in GB3635-1983, unless otherwise specified.

Under the optimal condition, the carrier provided by the invention has high mechanical strength and a better pore channel structure, can effectively improve the activity of the catalyst and the accessibility of an active center, and is very suitable for the diffusion of macromolecules.

According to the present invention, the ratio of the difference R between the water absorption of the carrier and the BET pore volume to the water absorption of the carrier is preferably 10 to 50%, more preferably 15 to 40%, and still more preferably 25 to 40%. The carrier provided by the invention has larger proportion, which shows that the proportion of macropores or super-macropores in the total pore volume of the carrier provided by the invention is larger. In the present invention, the pore volume of the carrier is measured by BET method and the water absorption (wiping-dry water absorption) of the carrier is measured by water absorption method without specific description, and the difference R between the water absorption and the BET pore volume is represented by the pore volume of macropores or macropores and the water absorption is represented by the total pore volume of the carrier.

The catalyst support may have various shapes depending on the particular application. For example, the catalyst support may be spherical, strip-shaped, ring-shaped, honeycomb-shaped, or butterfly-shaped. The strip shape mentioned in the invention can be a cylindrical strip, an elliptical strip (equivalent to a double-leaf strip) or a multi-leaf strip, and the shape of the strip shape is not limited in any way. The spherical shape mentioned in the invention can be a regular spherical shape or an irregular spherical shape, namely, the outline curve of the cross section of the catalyst carrier can be a circular shape or an imperfect circular shape. The invention does not limit the length and distribution of the strip-shaped carrier.

Preferably, the carrier is spherical and/or bar-shaped, more preferably bar-shaped, and still more preferably multilobal bar-shaped. In the present invention, the carrier is in the form of a multilobal strip, which means that the cross-sectional shape of the carrier is multilobal. The invention does not limit the size of each blade of the multilobal shape and the proportion of the size of each blade to other blades, namely the multilobal shape can be a regular multilobal shape, a non-regular multilobal shape or a deformed multilobal shape.

According to the present invention, the multi-lobar strips may be at least one of three-lobar strips, four-lobar strips, five-lobar strips, six-lobar strips, and the like.

According to a preferred embodiment of the invention, the support is spherical and/or in the form of a rod, the equivalent diameter of the support being not more than 5mm, preferably not more than 3mm, more preferably not more than 2mm, still more preferably 0.8-2 mm.

According to one embodiment of the invention, if the carrier is otherwise shaped, the minimum cross-sectional dimension of the outer shape of the carrier is not more than 5mm, preferably not more than 3mm, more preferably not more than 2 mm.

According to a preferred embodiment of the present invention, the bulk ratio of the carrier is 0.35 to 0.55g/mL, more preferably 0.40 to 0.50 g/mL. The carrier provided by the invention has a lower bulk ratio.

In the invention, the bulk ratio of the carrier is determined by a conventional method, and the specific method comprises the following steps: crushing the carrier, screening the carrier to obtain 16-20 mesh particles, taking a 500mL measuring cylinder, pouring the screened particles into the measuring cylinder, weighing the weight G and the visual volume V, and obtaining the bulk ratio G/V.

In the present invention, the composition of the catalyst support may be a composition conventional in the art, and may contain at least one of a refractory inorganic oxide and a molecular sieve.

The specific type of the heat-resistant inorganic oxide is not particularly limited in the present invention, and may be a heat-resistant inorganic oxide generally used in the art. For example, the heat-resistant inorganic oxide may be at least one selected from the group consisting of alumina, silica, titania, magnesia, zirconia, thoria and beryllia. Specific examples thereof may include, but are not limited to, alumina, silica, zirconia, titania, magnesia, thoria, beryllia, alumina-titania, alumina-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina-titania or silica-alumina-magnesia. Preferably, the heat-resistant inorganic oxide is at least one of alumina, silica, titania and zirconia. More preferably, the heat-resistant inorganic oxide is alumina.

The alumina mentioned in the invention refers to available mAl₂O₃·nH₂O represents a compound of its composition, wherein m and n are arbitrary numbers, and may be integers or fractions. The present invention also does not impose any limitation on the crystalline phase of the alumina.

The molecular sieve of the present invention refers to a material with regular crystal structure and pore channels, which is generally called molecular sieve or zeolite, and the molecular sieve or zeolite has a framework composed of silicon-aluminum elements, and may also contain other elements, such as: at least one of P, Ti, Ge and Ga. The invention is not limited in any way as to the composition of the elements that make up the molecular sieve.

The molecular sieve of the invention can be one type, or two or more types, or mixed crystal and twin crystal of two molecular sieves. The two molecular sieves described in the present invention refer to two different types of molecular sieves, and may be one molecular sieve, but the two molecular sieves have different properties (e.g., different silica-alumina ratios).

The two or more molecular sieves referred to in the present invention are 3 or more molecular sieves, and these molecular sieves may be different types of molecular sieves or the same type of molecular sieves having different properties. The amount of each molecular sieve may be between 0.1 and 80 wt% (based on the catalyst support).

The ratio of the two molecular sieves can be 10:1 to 1:10, 5:1 to 1:5, 3:1 to 1:3, 2:1 to 1:2, 1:1 and the like, and the ratio of the two molecular sieves is arbitrary.

According to the present invention, the molecular sieve may be selected from at least one of ten-membered ring silicoaluminophosphate molecular sieves, twelve-membered ring silicoaluminophosphate molecular sieves, fourteen-membered ring silicoaluminophosphate molecular sieves, and eighteen-membered ring silicoaluminophosphate molecular sieves. The invention does not limit the size of the pore opening and the pore diameter of the molecular sieve.

The invention has no limitation on the silicon-aluminum ratio of the molecular sieve, wherein the silicon-aluminum ratio refers to SiO₂/Al₂O₃。

According to a preferred embodiment of the present invention, the molecular sieve is selected from at least one of a ZRP molecular sieve, a Y molecular sieve, a beta molecular sieve, mordenite, a ZSM-5 molecular sieve, an MCM-41 molecular sieve, an omega molecular sieve, a ZSM-12 molecular sieve and an MCM-22 molecular sieve, and is further preferably at least one of a Y molecular sieve, a beta molecular sieve, a ZSM-5 molecular sieve and mordenite.

The molecular sieve of the invention can be obtained commercially or prepared by any conventional method.

The Y molecular sieve can be a Y molecular sieve with a cell constant of 2.452-2.475 nanometers and a silica/alumina molar ratio of 3.5-7; can be an ultra-stable Y molecular sieve prepared by performing one or more times of hydrothermal treatment after exchanging the Y molecular sieve with ammonium ions, wherein the unit cell constant of the Y molecular sieve is 2.420-2.455 nanometers, and the molar ratio of silicon oxide to aluminum oxide in a framework can reach 100, preferably 60; or the phosphorus-containing ultrastable Y molecular sieve is prepared by exchanging the Y molecular sieve with one or more inorganic ammonium solutions of phosphide and then carrying out one or more times of hydrothermal treatment; or the rare earth Y molecular sieve is prepared by combining the rare earth compound aqueous solution treatment Y molecular sieve with one or more hydrothermal treatments.

According to a preferred embodiment of the present invention, the content of the heat-resistant inorganic oxide is 1 to 99% by weight, more preferably 70 to 99% by weight, based on the total amount of the support; the content of the molecular sieve is 1 to 99% by weight, more preferably 1 to 30% by weight; more preferably, the refractory inorganic oxide is alumina and the molecular sieve is a Y molecular sieve.

In a second aspect, the present invention provides a method for preparing a catalyst carrier, the method comprising:

(1) mixing a carrier precursor, a foaming agent, water, an optional extrusion aid and an optional adhesive to obtain a mixture, kneading and molding;

(2) and (2) roasting the formed product obtained in the step (1).

According to the invention, the term "optional" means that it may or may not be added. In the mixing process in the step (1), the extrusion aid can be added or not added, and the adhesive can be added or not added.

According to the production method provided by the present invention, the carrier precursor is any substance that can be converted into a carrier by the firing in step (2). Specifically, the support precursor may be selected from at least one of refractory inorganic oxide, refractory inorganic oxide precursor, and molecular sieve. The heat-resistant inorganic oxide precursor is any substance that can be converted into a heat-resistant inorganic oxide by the firing in step (2). The refractory inorganic oxide is selected as described above, and the present invention is not described herein again.

The selection of the molecular sieve is as described above and the present invention is not described herein in detail.

According to the preparation method provided by the invention, the refractory inorganic oxide and/or the precursor of the refractory inorganic oxide and the molecular sieve are/is preferably used in an amount such that the content of the refractory inorganic oxide in the prepared carrier is 1 to 99 wt%, and more preferably 70 to 99 wt%, based on the total amount of the carrier; the content of the molecular sieve is 1 to 99% by weight, more preferably 1 to 30% by weight; more preferably, the refractory inorganic oxide is alumina and the molecular sieve is a Y molecular sieve.

According to the present invention, specific examples of the precursor of the alumina may include, but are not limited to: hydrated alumina (e.g., aluminum hydroxide, pseudoboehmite), gels containing hydrated alumina, and sols containing hydrated alumina. For example, the precursor of the alumina may be a dry glue powder. The dry rubber powder may be obtained commercially (for example, from catalyst Changjingtie), or may be prepared by any conventional method, and the present invention is not particularly limited thereto.

According to the invention, the foaming agent has the capability of encapsulating gas, and can be organic matter, inorganic matter, pure chemical substance or mixture of multiple components. The foaming agent may be selected from at least one of a physical foaming agent, a chemical foaming agent, a synthetic surfactant foaming agent, an animal protein foaming agent, and a plant foaming agent. Preferably, the foaming agent is an animal protein foaming agent and/or a plant foaming agent. The animal protein foaming agent is preferably at least one selected from the group consisting of an animal hoof and horn foaming agent, an animal hair foaming agent, and an animal blood gel foaming agent. The plant foaming agent is preferably at least one selected from rosin soap foaming agent, tea saponin and tea saponin.

According to a preferred embodiment of the invention, the foaming agent is an animal protein foaming agent, such as an animal hoof and horn foaming agent and/or egg white. The inventor of the present invention found in the research process that in the preparation process of the carrier, the animal protein foaming agent has obvious advantages in toughness and stability of the bubbles compared with the traditional physical foaming agent, chemical foaming agent and synthetic surfactant foaming agent.

According to the preparation method provided by the invention, the foaming agent can be introduced in the form of solution, water can be used as a solvent, other organic matters can also be used as a solvent, and water is preferred.

According to a preferred embodiment of the present invention, the animal protein foaming agent is introduced in the form of a hydrolysate of the animal protein foaming agent. When protein is hydrolyzed, protein macromolecules of longer peptide chains are changed into soluble small and medium molecular mixtures of short chains, and after the mixture is dissolved in water, a colloidal solution with certain viscosity can be formed.

The method for obtaining the animal protein foaming agent hydrolysate by hydrolyzing the animal protein foaming agent is not particularly limited in the present invention, and those skilled in the art can prepare the animal protein foaming agent hydrolysate by any means on the basis of the above description. For example, the method can be carried out according to the method disclosed in marxiyun, leizuyun, mathematic mine, et al, research on protein-type concrete foaming agents [ J ]. architecture science, 2009,25(5):73-76.

In order to promote the hydrolysis of the animal protein, a hydrolysis promoter may be suitably added during the hydrolysis, and the present invention is not particularly limited thereto.

According to the method provided by the invention, preferably, the extrusion aid is at least one selected from sesbania powder, cellulose and derivatives thereof, starch and derivatives thereof, ethylene glycol and diethylene glycol. The derivative of the starch can be one or more of oxidized starch, esterified starch, carboxymethyl starch, cationic starch, hydroxyalkyl starch and multi-component starch; the derivative of cellulose may be one or more of cellulose ether, cellulose ester and cellulose ether ester. The extrusion aid in the embodiment of the invention is exemplified by sesbania powder, and the invention is not limited thereto.

According to the method provided by the invention, the selection range of the type of the adhesive is wide, and the adhesive can be at least one of hydroxymethyl cellulose, inorganic acid, starch and derivatives thereof, silica sol and aluminum sol.

According to the method of the present invention, the specific manner of mixing the carrier precursor, the foaming agent, water, and optionally the extrusion aid, and optionally the binder is not particularly limited as long as the carrier precursor, the foaming agent, water, and optionally the extrusion aid, and optionally the binder are mixed. Preferably, the mixing of step (1) comprises: mixing the carrier precursor and the extrusion aid, and then adding the foaming agent, the adhesive and the water to obtain the mixture. In the preferred embodiment, the carrier precursor and the extrusion aid are mixed to obtain mixed powder, and then the foaming agent, the adhesive and the water are added, so that the catalytic performance of the catalyst prepared from the obtained carrier can be improved.

More preferably, the mixing of step (1) comprises: mixing the carrier precursor and the extrusion aid to obtain mixed powder; foaming a foaming agent, an adhesive and water to obtain a foaming liquid; and mixing the mixed powder and the foaming liquid. In this preferred embodiment, it is more advantageous to improve the catalytic performance of the catalyst obtained from the resulting support. The foaming may be accomplished in a blowing agent.

According to the invention, preferably, the foaming agent is an animal protein foaming agent, and the amount of the foaming agent is 0.5-20mL, preferably 1.0-10mL, relative to 100g of the carrier precursor on a dry basis. With such an advantageous embodiment, it is more advantageous to have a carrier that combines a higher mechanical strength with a better pore structure.

According to the invention, the blowing agent is preferably a plant blowing agent, which is used in an amount of 0.1 to 5g, for example 1 to 4g, relative to 100g of carrier precursor on a dry basis. With such an advantageous embodiment, it is more advantageous to have a carrier that combines a higher mechanical strength with a better pore structure.

According to the present invention, preferably, the amount of the extrusion aid is 0.1 to 6g, preferably 2 to 4g, relative to 100g of the carrier precursor on a dry basis.

According to the present invention, it is preferable that the binder is used in an amount of 0.1 to 10g relative to 100g of the carrier precursor on a dry basis.

According to the invention, the water in the mixture is used as a dispersing medium, and the amount of the water is based on the amount of the water capable of uniformly mixing the other components in the mixture.

According to the invention, the mixture may optionally also contain a peptizing agent, preferably no peptizing agent. In the existing catalyst carrier preparation process, a peptizing agent, such as dilute nitric acid, is required to be added, but the peptizing agent can be added or not added in the carrier preparation method provided by the invention.

According to the preparation method provided by the invention, the method comprises the following steps: and kneading and molding the mixture. Specifically, the mixture may be fed into an extruder, kneaded in the extruder, and extruded to obtain a molded product.

The mixture may be fed into an extruder for kneading and extrusion under conditions conventional in the art to give a shaped article.

The shape of the shaped article may be selected as described above with respect to the shape of the carrier, and the present invention is not described herein again.

In the present invention, the conditions for baking the shaped product are not particularly limited, and may be conventional conditions in the art. Generally, the temperature of the roasting may be 350-700 ℃, preferably 450-650 ℃; the calcination time may be 1 to 10 hours, preferably 2 to 6 hours. The calcination may be carried out in an oxygen-containing atmosphere (e.g., air) or in an inert atmosphere. The inert atmosphere refers to a gas that is inactive under the drying or firing conditions, for example: nitrogen and group zero element gases (e.g., argon).

Before the shaped object is baked, drying the shaped object can be further included, and the drying can be performed under the conventional conditions in the field, such as: the drying temperature may be 100-200 deg.C, and the drying time may be 2-12 hours. The drying may be performed under normal pressure or reduced pressure, and is not particularly limited. The drying may be performed in an oxygen-containing atmosphere or in an inert atmosphere.

The third aspect of the invention also provides a catalyst carrier prepared by the preparation method.

The catalyst carrier provided by the invention is suitable for being used as a carrier of various hydrogenation catalysts. The fourth aspect of the invention provides a hydrogenation catalyst, which comprises the carrier provided by the invention and a VIB group metal element and a VIII group metal element loaded on the carrier. The carrier and the preparation method thereof have been described in detail in the foregoing, and are not described herein again.

The group VIB metal element and the group VIII metal element may be supported on the carrier in various forms that are conventional in the art, respectively, such as: the group VIB metal element and the group VIII metal element may be supported on the carrier in the form of oxides, respectively.

The loading amounts of the group VIB metal elements and the group VIII metal elements may be conventionally selected in the art. Generally, the group VIB metal element may be present in an amount of 10 to 40 wt.%, preferably 15 to 30 wt.%, calculated as oxide, based on the total amount of the catalyst; the content of the group VIII metal element may be 2 to 10% by weight, preferably 2.5 to 7% by weight; the carrier may be present in an amount of 50 to 88 wt%, preferably 63 to 82.5 wt%.

The catalyst provided by the present invention can be prepared by various methods commonly used in the art as long as the carrier provided by the present invention is used as a carrier.

For example, the group VIB metal element and the group VIII metal element may be supported on the carrier by impregnating the carrier with a solution containing a compound of the group VIB metal element and a solution containing a compound of the group VIII metal element, and drying and calcining the carrier on which the above two compounds are supported. The group VIB metal element compound and the group VIII metal element compound may be selected according to the kinds of the group VIB metal element and the group VIII metal element, respectively. When the group VIB metal element is molybdenum and/or tungsten, the compound of the group VIB metal element may be a compound of tungsten and/or a compound of molybdenum. In the present invention, examples of the compound of the group VIB metal element may be, but are not limited to: one or more of tungstic acid, molybdic acid, metatungstic acid, ethyl metatungstic acid, paramolybdic acid, ammonium molybdate, ammonium paramolybdate, ammonium metatungstate and ammonium ethyl metatungstate. When the group VIII metal element is cobalt and/or nickel, the compound of the group VIII metal element is preferably one or more of an oxysalt using nickel as a cation, an oxysalt using cobalt as a cation, and an oxysalt using cobalt as a cation. In the present invention, examples of the compound of the group VIII metal element may be, but are not limited to: one or more of nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate, nickel chloride and cobalt chloride.

According to the present invention, various solvents commonly used in the art may be used to prepare the solution containing the compound of the group VIB metal element and the solution containing the compound of the group VIII metal element, as long as the compounds are soluble in the solvents to form a uniform and stable solution. For example: the solvent may be water or alcohol having 1 to 5 carbon atoms (e.g., ethanol), preferably water and/or ethanol, and more preferably water.

The impregnation method may be various impregnation methods commonly used in the art, and for example, may be a pore saturation impregnation method. The time for the impregnation and the number of times of the impregnation are not particularly limited in the present invention, as long as the amounts of the group VIB metal element and the group VIII metal element on the finally obtained catalyst can be ensured to meet specific use requirements. Generally, the time for the impregnation may be 0.5 to 12 hours.

According to the present invention, the conditions for drying the carrier loaded with the group VIB metal element and the group VIII metal element are not particularly limited. Generally, the temperature of the drying may be 80-300 ℃, preferably 100-; the drying time may be 0.5 to 24 hours, preferably 1 to 12 hours.

In the present invention, the conditions for calcining the dried carrier loaded with the group VIB metal element and the group VIII metal element are not particularly limited, and may be conventional conditions in the art. Generally, the temperature of the roasting may be 350-700 ℃, preferably 400-650 ℃; the calcination time may be 0.2 to 12 hours, preferably 1 to 10 hours. The calcination may be performed in an oxygen-containing atmosphere or in an inert atmosphere.

The hydrogenation catalyst provided by the invention can be used for hydrogenation reaction of various hydrocarbon raw materials, including but not limited to hydrodesulfurization, hydrodenitrogenation, olefin saturation, aromatic saturation, hydrocracking and hydroisomerization. The catalyst provided by the invention can also be used as an oxidation catalyst for aromatization reaction, photocatalytic reaction, immobilized enzyme and the like.

The hydrocarbon feedstock may be various heavy mineral oils or synthetic oils or their mixed distillates, such as straight run gas oils (straight run gas oil), vacuum gas oils (vacuum gas oil), demetallized oils (demetalized oils), atmospheric residues (atmospheric residues), deasphalted vacuum residues (deasphalted vacuum residues), coker distillates (coker distillates), catalytic cracker distillates (cat cracker distillates), shale oils (shell oils), tar sand oils (tar sand oil), and coal liquefaction oils (coal liquid).

The inventors of the present invention have found that the catalyst provided by the present invention is particularly suitable as a hydrocracking catalyst for hydrocracking various hydrocarbon oils to produce hydrocarbon fractions having a lower boiling point and a lower molecular weight.

According to a fifth aspect of the present invention, the present invention provides a hydrocracking method, comprising contacting a hydrocarbon oil with a hydrocracking catalyst under hydrocracking conditions, wherein the hydrocracking catalyst is the hydrocracking catalyst provided by the present invention.

The hydrogenation catalyst and the preparation method thereof have been described in detail above and will not be described in detail herein.

The hydrocarbon oil can be various hydrocracking raw materials commonly used in the field, and can be various heavy mineral oils, synthetic oils or mixtures thereof. Specifically, examples of the hydrocarbon oil may include, but are not limited to: vacuum gas oils, demetallized oils, atmospheric residues, deasphalted vacuum residues, coker distillates, shale oils, tar sand oils, and coal liquefaction oils.

The hydrocracking process of the present invention is not particularly limited with respect to the remaining conditions for hydrocracking, and may be conditions conventional in the art. Generally, the hydrocracking conditions include: the temperature can be 200-650 ℃, preferably 300-510 ℃; the pressure may be from 3 to 24 MPa, preferably from 4 to 15 MPa, expressed as gauge pressure; the volume ratio of the hydrogen to the oil can be 100-; the liquid hourly volume space velocity can be 0.1-30 h^-1Preferably 0.2 to 5 hours^-1。

According to the hydrocracking process of the present invention, the catalyst is preferably presulfided prior to use. The conditions of the prevulcanisation may be conventional in the art. For example, the conditions of the prevulcanisation may include: presulfiding with sulfur, hydrogen sulfide or a sulfur-containing feedstock in the presence of hydrogen at a temperature of 140 ℃ and 370 ℃. According to the hydrocracking process of the present invention, the presulfiding can be carried out either outside the reactor or in situ within the reactor.

The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

In the following examples, BET pore volume was measured according to the method specified in RIPP 151-90; the water absorption rate is wiping dry water absorption rate, the wiping dry water absorption rate is that the carrier which is dry is soaked in deionized water for 60 minutes at room temperature (20-25 ℃), the carrier is wiped dry by using filter paper after filtration, the mass of the carrier after water absorption is obtained, and the ratio of the mass difference of the carrier which does not absorb water to the carrier which does not absorb water is wiping dry water absorption rate; the radial crushing strength of the catalyst carrier was measured on a crushing strength tester of model QCY-602 (manufactured by alkali research, Ministry of chemical industry) according to the method specified in GB 3635-1983; the method for measuring the bulk ratio of the carrier comprises the following steps: crushing the carrier, screening the carrier to obtain 16-20 mesh particles, taking a 500mL measuring cylinder, pouring the screened particles into the measuring cylinder, weighing the weight G and the visual volume V, and obtaining the bulk ratio G/V.

In the following examples and comparative examples, the pressure is in gauge pressure and the dry content is determined by baking the sample at 600 ℃ for 4 hours.

Example 1

(1) Mixing dry rubber powder (obtained from catalyst Chang Ling division, 68 wt% on dry basis)The same applies to) 200.0g of HY molecular sieve (obtained from catalyst Chang Ling division, 79 percent of dry basis by weight, the same applies below) 63.7g of sesbania powder and 8g of sesbania powder are mixed uniformly to obtain mixed powder. Animal protein foaming agent (preparation method: cow hoof horn 20g, Ca (OH))₂6g，NaHSO₃2g, 200mL of water, 80 ℃ of hydrolysis temperature and 6h of hydrolysis time, and preparing foaming liquid from the following sources: study of maleichness, Liyun, Lexuri, Tezui, Jiayonghui, protein type concrete foaming agent [ J]Building science, 2009,25(05):73-76.)5mL (equivalent to 0.5g of cow hoof) and 1g of hydroxymethyl cellulose, water was added to 175mL, and after foaming was completed in a foaming machine, the mixture was mixed with the mixed powder to obtain a mixture. The mixture is sent into a strip extruding machine to be repeatedly kneaded for 3 times (15 minutes) and then adoptedExtruding the strips by a pore plate, drying the obtained extruded strips at 120 ℃ for 3 hours, and roasting the extruded strips at 600 ℃ for 3 hours under the condition of introducing air to obtain the catalyst carrier SSA.

(2) And (2) measuring the absorptivity of the catalyst carrier SSA, preparing a mixed aqueous solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, purchased from Changling catalyst factory) according to the tungsten oxide content of 19.5 wt% and the nickel oxide content of 5.5 wt% in the catalyst, and impregnating the catalyst carrier SSA prepared in the step (1) by adopting a pore saturation method. The impregnated carrier was dried at 120 ℃ for 5 hours, followed by calcination at 400 ℃ for 3 hours to obtain catalyst SCA.

(3) Evaluation of the catalyst prepared in step (2)

The one-pass process is adopted, and the raw oil adopts the properties of the Nominax VGO (2011): the density (20 ℃ C.) was 0.9122g/cm³，T_IBP＝272℃；T_50％＝422℃；T_FBP＝536℃。

Crushing the catalyst into particles with the length range of 3.0-5.0 mm, filling 100g of the catalyst into a 200ml fixed bed reactor, filling the residual space with porcelain balls, carrying out dry-method vulcanization on the catalyst for 28 hours by adopting DMDS as a vulcanizing agent under the conditions that the hydrogen partial pressure is 15.0MPa and the temperature is 300 ℃ before oil is introduced, and then introducing the catalyst into the reactor under the conditions that the hydrogen partial pressure is 14.7MPa and the temperature is 350 DEG CRaw oil is added, the hydrogen-oil ratio is 1200 volume/volume, and the liquid hourly space velocity is 0.85h^-1And a sample was taken after 400 hours of reaction.

The catalytic activity of the catalyst and the yield of aviation kerosene (distillation range 160-:

the activity refers to the cracking reaction temperature required when the conversion rate of the hydrocarbon oil with the distillation temperature higher than 350 ℃ is 60 percent, and the lower the cracking reaction temperature is, the higher the catalytic activity of the catalyst is;

the 95% temperature of the tail oil is the distillation temperature of the 95% distillation point in the simulated distillation curve.

Comparative example 1

(1) 200.0g of dry rubber powder, 63.7g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. 4.5mL of 68% nitric acid by weight was added to 175mL of water, mixed uniformly, and then added to the mixed powder, and mixed to obtain a mixture. The mixture is sent into a strip extruding machine to be repeatedly kneaded for 3 times (15 minutes) and then adoptedExtruding the strips by a pore plate, drying the obtained extruded strips at 120 ℃ for 3 hours, and roasting the extruded strips at 600 ℃ for 3 hours under the condition of introducing air to obtain the catalyst carrier DSA.

(2) Measuring the absorptivity of the catalyst carrier DSA, preparing a mixed aqueous solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, purchased from Changling catalyst factory) according to the tungsten oxide content of 19.5 wt% and the nickel oxide content of 5.5 wt% in the catalyst, and impregnating the catalyst carrier DSA prepared in the step (1) by adopting a pore saturation method. The impregnated carrier was dried at 120 ℃ for 5 hours, followed by calcination at 400 ℃ for 3 hours to obtain a catalyst DCA.

(3) The catalyst prepared in step (2) of comparative example 1 was evaluated in the same manner as in step (3) of example 1, and the results are shown in Table 2.

Example 2

(1) 200.0g of dry rubber powder, 63.7g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. Mixing egg white (10 mL) and hydroxymethyl cellulose 1g, and adding waterTo 175mL, after foaming in a foaming machine, the mixture was mixed with the mixed powder to obtain a mixture. The mixture is sent into a strip extruding machine to be repeatedly kneaded for 3 times (15 minutes) and then adoptedExtruding the strips by a pore plate, drying the obtained extruded strips at 120 ℃ for 3 hours, and roasting the extruded strips at 600 ℃ for 3 hours under the condition of introducing air to obtain the catalyst carrier SSB.

(2) And (2) measuring the absorptivity of the catalyst carrier SSB, preparing a mixed aqueous solution of nickel nitrate (analytically pure, Beijing Yili chemical reagent factory) and ammonium metatungstate (industrial product, purchased from Changling catalyst factory) according to the tungsten oxide content of 19.5 wt% and the nickel oxide content of 5.5 wt% in the catalyst, and impregnating the catalyst carrier SSB prepared in the step (1) by adopting a pore saturation method. The impregnated carrier was dried at 120 ℃ for 5 hours, followed by calcination at 400 ℃ for 3 hours to obtain a catalyst SCB.

(3) The catalyst prepared in step (2) of example 2 was evaluated in the same manner as in step (3) of example 1, and the results are shown in Table 2.

Example 3

The carrier and catalyst were prepared according to the method of example 1 except that the amount of the animal protein foaming agent was 10 mL. The carrier SSC and catalyst SCC are obtained. The evaluation results of the catalyst are shown in table 2.

Example 4

The carrier and catalyst were prepared according to the method of example 1 except that the amount of the animal protein foaming agent was 20 mL. Obtaining the carrier SSD and the catalyst SCD. The evaluation results of the catalyst are shown in table 2.

Example 5

A carrier and catalyst were prepared as in example 2, except that 20mL of egg white was used. Obtaining the carrier SSE and the catalyst SCE. The evaluation results of the catalyst are shown in table 2.

Example 6

(1) 200.0g of dry rubber powder, 63.7g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. Animal protein foaming agent (preparation method: cow hoof horn 20g, Ca (OH))₂ 6g，NaHSO₃2g, 200mL of water, 80 ℃ of hydrolysis temperature and 6h of hydrolysis time, and preparing foaming liquid from the following sources: study of maleichness, Liyun, Lexuri, Tezui, Jiayonghui, protein type concrete foaming agent [ J]Building science, 2009,25(05):73-76.)5mL, egg white (taken from fresh eggs) 5mL and hydroxymethyl cellulose 1g, water was added to 175mL, and after foaming in a foaming machine, the mixture was mixed with the mixed powder to obtain a mixture. The mixture is sent into a strip extruding machine to be repeatedly kneaded for 3 times (15 minutes) and then adoptedExtruding the strips by a pore plate, drying the obtained extruded strips at 120 ℃ for 3 hours, and roasting the extruded strips at 600 ℃ for 3 hours under the condition of introducing air to obtain the catalyst carrier SSF.

(2) The catalyst was prepared according to the procedure of example 1 to obtain the catalyst SCF.

(3) The catalyst prepared in step (2) was evaluated in the same manner as in step (3) of example 1, and the results are shown in Table 2.

Example 7

The process of example 1 was followed except that a plant foaming agent was used. Specifically, the method comprises the following steps:

(1) 200.0g of dry rubber powder, 63.7g of HY molecular sieve and 8g of sesbania powder are uniformly mixed to obtain mixed powder. Mixing 1.5g tea saponin (obtained from feihuang chemical Co., Ltd., New Yiyi) and 0.5mL nitric acid with a weight concentration of 68%, adding water to 175mL, foaming in a foaming machine, and mixing with the mixed powder to obtain a mixture. The mixture is sent into a strip extruding machine to be repeatedly kneaded for 3 times (15 minutes) and then adoptedExtruding the strips by a pore plate, drying the obtained extruded strips at 120 ℃ for 3 hours, and roasting the extruded strips at 600 ℃ for 3 hours under the condition of introducing air to obtain the catalyst carrier SSG.

(2) The catalyst was prepared according to the method of example 1 to obtain catalyst SCG.

(3) The catalyst prepared in step (2) was evaluated in the same manner as in step (3) of example 1, and the results are shown in Table 2.

The physicochemical properties of the support obtained above were characterized and the results are shown in table 1 below.

TABLE 1

Note: the ratio refers to the proportion of the difference R in the water absorption of the carrier; the strength refers to the radial crush resistance of the carrier.

TABLE 2

	Activity (. degree.C.)	Yield of aviation kerosene (%)	95% temperature/deg.C tail oil
				Example 1	369.8	37.9	492.1
Example 2	369.6	37.6	492.6
				Example 3	370.5	38.7	490.5
Example 4	372.0	40.3	486.5
				Example 5	370.0	38.1	491.6
Example 6	369.8	37.9	492.1
				Example 7	369.1	37.0	493.5
Comparative example 1	368.1	35.6	495.6

As can be seen from the results in Table 2, the catalyst prepared by using the carrier of the invention has the characteristics of high yield of aviation kerosene, higher activity, strong dry point reducing capability and the like.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.