CN115254082A - Catalyst carrier and preparation method thereof, catalyst and preparation method and application thereof - Google Patents
Catalyst carrier and preparation method thereof, catalyst and preparation method and application thereof Download PDFInfo
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- CN115254082A CN115254082A CN202110472480.1A CN202110472480A CN115254082A CN 115254082 A CN115254082 A CN 115254082A CN 202110472480 A CN202110472480 A CN 202110472480A CN 115254082 A CN115254082 A CN 115254082A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000011280 coal tar Substances 0.000 claims abstract description 59
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229960000892 attapulgite Drugs 0.000 claims abstract description 12
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000004523 catalytic cracking Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 241000219793 Trifolium Species 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 44
- 230000000694 effects Effects 0.000 abstract description 21
- 238000011068 loading method Methods 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000011156 evaluation Methods 0.000 description 15
- 239000003921 oil Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a carrier and a preparation method thereof, a catalyst and a preparation method and application thereof. The catalyst carrier comprises the following raw materials in percentage by mass: 20-40% of attapulgite and TiO2/Al2O360 to 80 percent. The catalyst carrier of the invention adopts attapulgite and TiO2/Al2O3The composite carrier can improve the capacity of loading active components, thereby improving the hydrogenation effect and the yield of light oil of the catalyst, and the catalyst is used for the lightening reaction of coal tar, can reduce the reaction cost and reduce the energy consumption, and has good industrialization prospect.
Description
Technical Field
The invention belongs to the technical field of hydrogenation catalysts in coal chemical industry, and particularly relates to a catalyst carrier and a preparation method thereof, and a catalyst and a preparation method and application thereof.
Background
Coal tar is a byproduct in coal coking, dry distillation and gasification processes, contains a large amount of aromatic and other cyclic compounds, is difficult to fully combust, and can cause serious pollution to the environment. With the improvement of the national ecological civilization construction and the increase of the environmental protection, how to produce high-clean fuel and high-value-added products by using the coal tar becomes a key research direction in the field of coal chemical industry. In the technology of preparing coal tar into clean fuel and high value-added products, the hydrogenation technology has unique advantages, fuel oil and high value-added products can be prepared in a hydrogenation mode, and the research on the high value-added core products mainly refers to the research and development and application of the hydrogenation catalyst.
CN101633848B discloses a medium and low temperature coal tar deep processing method to obtain dry gas, liquefied gas, hydrogenated naphtha and hydrogenated diesel, but the process is only applicable to medium and low temperature coal tar, is not applicable to high temperature coal tar, and simultaneously, tail-removed pitch is not fully utilized, so that the yield of light oil is low. CN1351130A discloses a method for producing diesel oil from coal tar, which mainly comprises the steps of fractionating coal tar, wherein the obtained heavy fraction is not used as a raw material for hydrogenation treatment, but naphtha and diesel oil fraction in the coal tar are subjected to hydrogenation treatment, so that the treatment easily results in low yield of light oil. CN110643391A discloses a method for converting coal tar into liquefied gas, naphtha and diesel oil, which adopts a suspension bed, has higher investment, higher operating temperature and pressure and large energy consumption.
Therefore, the method has important practical significance on how to improve the yield of the light oil and the impurity resistance of the product and reduce the reaction cost.
Disclosure of Invention
The invention aims to solve the technical problems of low yield of light oil, weak impurity resistance of a product, high reaction cost and high energy consumption in the prior art.
In order to achieve the object of the present invention, in a first aspect, the present invention provides a catalyst carrier,based on the mass of the carrier, the carrier comprises the following raw materials in percentage by mass: attapulgite clay 20% -40%, such as in the range of 25% -35%,20%,30%,40%, and any combination thereof, and TiO2/Al2O3Ranges of 60% -80%, such as 65% -75%,60%,65%,70%,75%,80%, and any combination thereof.
The catalyst carrier of the invention adopts attapulgite and TiO2/Al2O3The composite carrier can improve the capacity of loading active components, thereby improving the hydrogenation effect and the yield of light oil of the catalyst, and the catalyst is used for the lightening reaction of coal tar, can reduce the reaction cost and reduce the energy consumption, and has good industrialization prospect.
In addition, al can be adjusted2O3With TiO2The ratio of (a) to (b) further improves the ability of the carrier to carry the active ingredient. In the present invention, al2O3With TiO2In a mass ratio of 3 to 5, for example 4 to 4.5:1, 3.5.
As a specific embodiment of the present invention, the carrier is in the shape of clover. The clover-shaped carrier can increase the appropriate specific surface area.
In a second aspect, the present invention provides a catalyst comprising a catalyst carrier as claimed.
The catalyst of the invention adopts attapulgite and TiO2/Al2O3The composite carrier improves the capacity of loading active components, improves the hydrogenation effect and the yield of light oil of the catalyst, and has good industrialization prospect by applying the catalyst to the lightening reaction of coal tar, thereby reducing the reaction cost and reducing the energy consumption.
The desired catalytic effect of the catalyst can be obtained by impregnation of the active component into the support. In the invention, the nickel oxide is further included in an amount of 10 to 20 mass% based on the mass of the carrier. The non-noble metal nickel is used as an active component to modify the carrier, so that the hydrogenation effect can be further improved, and the production cost is greatly reduced.
In a third aspect, the present invention provides a method for preparing the above catalyst carrier.
The preparation method of the catalyst carrier comprises the following steps:
mixing Al2O3Impregnating the raw material with a titanium salt solution, and roasting to prepare TiO2/Al2O3；
Subjecting the TiO to a reaction2/Al2O3Mixing with attapulgite, adding into nitric acid solution, kneading, molding, and calcining to obtain the catalyst carrier.
In the present invention, it is also possible to obtain carriers of different shapes, for example clover shapes, by means of a plodder using a template.
The preparation method of the catalyst carrier of the invention is to impregnate Al on the catalyst carrier2O3The titanium component is added, and then the titanium component and the attapulgite are mixed and molded to obtain the composite carrier, so that the capability of loading the active component is improved, and the hydrogenation effect and the yield of light oil of the catalyst are further improved. The catalyst is used for the coal tar lightening reaction, can reduce the reaction cost and the energy consumption, and has good industrialization prospect.
The property of the carrier can be reasonably controlled by further designing reaction raw materials or processes. As a specific embodiment of the present invention, the Al2O3The specific surface area of the raw material was about 150m2/g-200m2G, e.g. 160m2/g-190m2/g，170m2/g-180m2(iv) g. The pore volume may be 0.01mL/g to 0.05mL/g,0.05mL/g to 0.1mL/g,0.1mL/g to 0.5mL/g,0.5mL/g to 1mL/g,1mL/g to 1.5mL/g,1.5mL/g to 2mL/g. The pore volume in the present invention means the volume of micropores (excluding macropores). Ensuring the proportion of micropores within the above range ensures the strength of the catalyst.
Specifically, in the impregnation step, the impregnation time may be in the range of 5h to 7h, for example, 5.5h to 6.5h,5h,5.5h,6h,6.5h,7h, and any combination thereof.
The impregnation temperature may be set to normal temperature. The impregnation method is not particularly limited, and the carrier may be immersed in the impregnation solution, or the impregnation solution may be sprayed or applied to the surface of the carrier to impregnate the carrier, which is within the scope of the present invention.
In the embodiment of the present invention, for the purpose of pore-enlarging and preventing the molecular sieve from being blocked, the carrier may be subjected to acid treatment, the acid solution used in the acid treatment may have a concentration of 1% to 5%, such as 2% to 4%, and the acid solution is generally an inorganic acid, such as nitric acid, hydrochloric acid, sulfuric acid, etc., such as nitric acid, so as to achieve the purpose of regulating the acidity and the pore structure of the molecular sieve, especially regulating the acid distribution of the molecular sieve and moderately enlarging the pores
In general, a drying step may also be included in the preparation of the catalyst support. For example, in the reaction of Al2O3After the raw material is impregnated with the titanium salt solution, the drying operation can be carried out firstly, and the drying temperature is generally 100-140 ℃, for example, 105-130 ℃, 110-120 ℃; the drying time may be from 6h to 12h, for example from 8h to 10h.
The firing operation is then performed at a firing temperature that may range from 500 ℃ to 800 ℃, such as 600 ℃ to 700 ℃,550 ℃,650 ℃,750 ℃, and any combination thereof. The calcination time may range from 3h to 5h, such as 3.5h to 4.5h,3h,3.5h,4h,4.5h,5h, and any combination thereof.
As a specific embodiment of the present invention, the titanium salt may be at least one selected from acetate, sulfate and nitrate salts of titanium, and the present invention is not particularly limited thereto.
In a fourth aspect, the invention provides a method for preparing the catalyst.
The preparation method of the catalyst comprises the following steps:
mixing Al2O3The raw material is dipped by titanium salt solution and is roasted to prepare TiO2/Al2O3；
Subjecting the TiO to a reaction2/Al2O3Mixing with attapulgite, adding into nitric acid solution, kneading, molding, and calcining to obtain catalyst carrier;
by NH4Cl solutionAnd (2) carrying out ammonium ion exchange on the catalyst carrier, filtering and washing, impregnating the catalyst carrier with a nickel salt solution, and roasting to prepare the catalyst.
The preparation method of the catalyst of the invention is to impregnate Al on Al2O3The catalyst is used for the coal tar lightening reaction, so that the reaction cost can be reduced, the energy consumption is reduced, and the catalyst has a good industrial prospect.
In particular embodiments of the invention, where the ammonium ion exchange treatment is performed, NH may be employed at a concentration of about 0.1g/mL to 1g/mL, such as 0.3g/mL to 0.7g/mL4The carrier is ammonium exchanged with a solution of Cl at a temperature of about 90 ℃ to 110 ℃, e.g. 95 ℃ to 105 ℃, for a period of 2h to 6h, e.g. 3h to 5h. The mass ratio of the carrier to the ammonium ion solution is 1. The ammonium ion solution with proper concentration is utilized, and the control of the treatment condition is combined, so that the regulation and control of the pore structure and the acid property of the catalyst can be realized, and the selectivity and the yield of the catalyst can be effectively improved.
In a fifth aspect, the invention provides an application of the catalyst in coal tar lightening.
The application of the catalyst in the lightening of coal tar comprises the following steps: carrying out catalytic cracking reaction on coal tar and hydrogen under the action of the catalyst; wherein, the volume ratio of hydrogen to coal tar is 800-1000, such as 830-970:1, 850; the reaction temperature is 230 ℃ to 340 ℃, such as 240 ℃ to 280 ℃,250 ℃ to 320 ℃,270 ℃ to 300 ℃,235 ℃,265 ℃,285 ℃,305 ℃,325 ℃,340 ℃ and any combination thereof; reaction pressures in the range of from 2MPa to 5MPa, for example, from 3MPa to 4MPa, from 2.5MPa to 3.5MPa,2MPa,2.5MPa,3MPa,3.5MPa,4MPa,4.5MPa,5MPa, and any combination thereof; the feed space velocity is 0.2h-1-3h-1E.g. 0.5h-1-2h-1，1h-1-1.5h-1，2h-1-3h-1。
The space velocity in the present invention means a liquid phase volume space velocity.
The application of the catalyst in the coal tar lightening is to use the coal tar as a raw material and carry out catalytic cracking reaction by adopting the catalyst, thereby improving the hydrogenation effect and the light oil yield of the catalyst, reducing the reaction cost and the energy consumption and having good industrialization prospect.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
The test methods in examples and comparative examples of the present invention are as follows:
1. specific surface area test: multiple BET specific surface area by nitrogen adsorption
2. And (3) testing the pore volume: determination of pore volume by carbon tetrachloride method
The coal tar of the examples and comparative examples of the present invention was derived from a coal chemical plant. The reaction apparatus used is a suitable reaction apparatus known to the person skilled in the art, for example a fixed isothermal bed hydrogenation reaction apparatus.
Examples 1 to 6
Example 1
Example 1 proposes a catalyst support and catalyst, the preparation method of which comprises the following steps:
1. preparation of catalyst support
100g of the powder had a specific surface area of 160m2Cylindrical alumina/g and pore volume of 0.74mL/g was impregnated with 50mL of titanium sulfate in 0.6g/mL dilute sulfuric acid solution for 6h, dried at a temperature of 110 ℃ for 10h, and calcined at a temperature of 600 ℃ for 4h to obtain 125g of alumina-titania support, wherein the weight ratio of alumina to titania was 4. Mixing a certain amount of attapulgite with a certain amount of TiO2/Al2O3Mixing, adding 2% nitric acid water solution, kneading, extruding, drying at 120 deg.C, and baking at 700 deg.C in air for 4 hr to obtain the composite carrier.
2. Preparation of the catalyst
Taking the above compoundMixing with carrier, and adding 0.5g/mL NH at 100 deg.C4The carrier is ion exchanged for 4h with 20mL Cl solution, filtered, washed and dried at 120 ℃. Then soaking the catalyst in a nickel nitrate solution, filtering, drying for 8 hours at the temperature of 120 ℃, and roasting for 4 hours at the temperature of 700 ℃ in the air to obtain the catalyst A.
Examples 2 to 6
Examples 2-6 catalyst supports and catalysts were prepared according to the method of example 1, with the catalyst numbers B, C, D, E, F in that order. The differences of the parameters are shown in Table 1.
TABLE 1 catalyst parameters for examples 1-6
Example 7
Loading a catalyst A into a 100mL isothermal bed hydrogenation reaction evaluation device, and carrying out catalytic cracking reaction on coal tar and hydrogen under the action of the catalyst A; wherein the volume ratio of hydrogen to coal tar is 300-1The hydrogenation effect of the coal tar is shown in Table 2.
Example 8
Loading a catalyst A into a 100mL isothermal bed hydrogenation reaction evaluation device, and carrying out catalytic cracking reaction on coal tar and hydrogen under the action of the catalyst A; wherein the volume ratio of hydrogen to coal tar is 400 to 1, the reaction temperature is 300 ℃, the reaction pressure is 2.5MPa, and the feeding airspeed is 1.0h-1The hydrogenation effect of the coal tar is shown in Table 2.
Example 9
A 100mL isothermal bed hydrogenation reaction evaluation device is used, a catalyst B is filled in the device, and coal tar and hydrogen are subjected to catalytic cracking reaction under the action of the catalyst B; wherein the volume ratio of hydrogen to coal tar is 3502h-1The hydrogenation effect of coal tar is shown in Table 2.
Example 10
Loading a catalyst B into a 100mL isothermal bed hydrogenation reaction evaluation device, and carrying out catalytic cracking reaction on coal tar and hydrogen under the action of the catalyst B; wherein the reaction temperature is 280 ℃, the reaction pressure is 3.5MPa, and the feeding airspeed is 2h-1The hydrogenation effect of the coal tar is shown in Table 2.
Example 11
A 100mL isothermal bed hydrogenation reaction evaluation device is used, a catalyst B is filled in the device, and coal tar and hydrogen are subjected to catalytic cracking reaction under the action of the catalyst B; wherein the reaction temperature is 280 ℃, the reaction pressure is 5.0MPa, and the feeding airspeed is 1h-1The hydrogenation effect of the coal tar is shown in Table 2.
Example 12
Loading a catalyst C into a 100mL isothermal bed hydrogenation reaction evaluation device, and carrying out catalytic cracking reaction on coal tar and hydrogen under the action of the catalyst C; wherein the reaction temperature is 260 ℃, the reaction pressure is 3.0MPa, and the feeding airspeed is 0.8h-1The hydrogenation effect of the coal tar is shown in Table 2.
Example 13
A 100mL isothermal bed hydrogenation reaction evaluation device is used, a catalyst C is filled, and coal tar and hydrogen are subjected to catalytic cracking reaction under the action of the catalyst C; wherein the reaction temperature is 280 ℃, the reaction pressure is 3.5MPa, and the feeding airspeed is 1.0h-1The hydrogenation effect of the coal tar is shown in Table 2.
Example 14
Loading a catalyst D into a 100mL isothermal bed hydrogenation reaction evaluation device, and carrying out catalytic cracking reaction on coal tar and hydrogen under the action of the catalyst D; wherein the reaction temperature is 340 ℃, the reaction pressure is 2.5MPa, and the feeding airspeed is 0.5h-1The hydrogenation effect of coal tar is shown in Table 2.
Example 15
A 100mL isothermal bed hydrogenation reaction evaluation device is used, a catalyst D is filled, and coal tar and hydrogen are subjected to catalytic cracking reaction under the action of the catalyst D; wherein the reaction temperature isAt 270 ℃, the reaction pressure is 4.0MPa, and the feeding airspeed is 1.0h-1The hydrogenation effect of the coal tar is shown in Table 2.
Example 16
Loading a catalyst E into a 100mL isothermal bed hydrogenation reaction evaluation device, and carrying out catalytic cracking reaction on coal tar and hydrogen under the action of the catalyst E; wherein the reaction temperature is 340 ℃, the reaction pressure is 2.0MPa, and the feeding airspeed is 2.5h-1The hydrogenation effect of coal tar is shown in Table 2.
Example 17
A 100mL isothermal bed hydrogenation reaction evaluation device is used, a catalyst E is filled, and coal tar and hydrogen are subjected to catalytic cracking reaction under the action of the catalyst E; wherein the reaction temperature is 300 ℃, the reaction pressure is 2.0MPa, and the feeding airspeed is 1.0h-1The hydrogenation effect of the coal tar is shown in Table 2.
Example 18
A 100mL isothermal bed hydrogenation reaction evaluation device is used, a catalyst F is filled, and coal tar and hydrogen are subjected to catalytic cracking reaction under the action of the catalyst F; wherein the reaction temperature is 270 ℃, the reaction pressure is 3.0MPa, and the feeding airspeed is 3.0h-1The hydrogenation effect of the coal tar is shown in Table 2.
Example 19
A 100mL isothermal bed hydrogenation reaction evaluation device is used, a catalyst F is filled, and coal tar and hydrogen are subjected to catalytic cracking reaction under the action of the catalyst F; wherein the reaction temperature is 240 ℃, the reaction pressure is 2.5MPa, and the feeding airspeed is 2.0h-1The hydrogenation effect of coal tar is shown in Table 2.
The above examples and comparative examples were tested or calculated using the following methods:
yield = oil containing alkanes and cycloalkanes/crude oil x 100%
Yield = [ (liquefied gas mass + naphtha mass + diesel mass)/coal tar mass ] × 100%
Space velocity of feed = feed per hour/mass of catalyst
TABLE 2 coal tar hydrogenation effect of different catalysts
Note: light oil here refers to a ratio containing saturated alkanes. The coal tar contains paraffin, cyclane, olefin, and a large amount of polycyclic aromatic hydrocarbon and derivatives, and after hydrogenation, the olefin is saturated, and the polycyclic aromatic hydrocarbon derivatives are deoxidized and denitrified to generate light oil.
Comparative example 1
Two sets of 100mL fixed isothermal bed hydrogenation reaction evaluation devices are used for respectively loading a catalyst C and an existing catalyst (the carrier is Gamma-Al)2O3The active component is NiO 2.5 percent; WO320%) and using the same process conditions to lighten the coal tar, wherein the process conditions are as follows: the reaction temperature is 280 ℃, the reaction pressure is 3.0MPa, and the space velocity is 1.0h-1The hydrogenation effect is shown in Table 3.
TABLE 3 comparison of hydrogenation Performance of the catalyst with the imported catalyst
| Name of catalyst | Catalyst C | Existing catalysts |
| Yield of light oil (%) | 94.6 | 84.5 |
As can be seen from table 3, under the same evaluation conditions, the light oil yield was significantly increased using the catalyst as compared to the coal tar lightened using the prior catalyst.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or the value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88, 8230, and 69 to 71 and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst carrier is characterized by comprising the following raw materials in percentage by mass based on the mass of the carrier: 20 to 40 percent of attapulgite and TiO2/Al2O3 60％-80％。
2. The catalyst carrier according to claim 1, wherein Al is2O3With TiO2The mass ratio of (A) to (B) is 3-5; preferably, al2O3With TiO2The mass ratio of (A) to (B) is 4-4.5.
3. A catalyst carrier according to claim 1 or 2 in the form of a clover.
4. A catalyst comprising the catalyst support of any one of claims 1 to 3.
5. The catalyst according to claim 4, further comprising 10 to 20 mass% of nickel oxide based on the mass of the carrier.
6. A method for producing a catalyst carrier according to any one of claims 1 to 3, characterized by comprising the steps of:
mixing Al2O3Impregnating the raw material with a titanium salt solution, and roasting to prepare TiO2/Al2O3；
Mixing the TiO with a solution of a binder2/Al2O3Mixing with attapulgite, adding into nitric acid solution, kneading, molding, and calcining to obtain the catalyst carrier.
7. The method of claim 6, wherein the Al is2O3The specific surface area of the raw material was 150m2/g-200m2The pore volume is 0.01mL/g-2mL/g.
8. The method according to claim 6 or 7, characterized in that in the impregnation step, the impregnation time is 5h to 7h;
the mass concentration of the nitric acid solution is 1-5%.
9. A process for preparing the catalyst according to claim 4 or 5, comprising the steps of:
mixing Al2O3Impregnating the raw material with a titanium salt solution, and roasting to prepare TiO2/Al2O3；
Mixing the TiO with a solution of a binder2/Al2O3Mixing with attapulgite, adding into nitric acid solution, kneading, molding, and calciningThen preparing a catalyst carrier;
by NH4And (3) carrying out ammonium ion exchange on the catalyst carrier by using a Cl solution, soaking the catalyst carrier by using a nickel salt solution after filtering and washing, and roasting to prepare the catalyst.
10. The application of the catalyst of claim 4 or 5 in coal tar lightening is characterized by comprising the following steps: carrying out catalytic cracking reaction on coal tar and hydrogen under the action of the catalyst; wherein the volume ratio of hydrogen to coal tar is 800-1000, the reaction temperature is 230-340 ℃, the reaction pressure is 2-5 MPa, and the feeding airspeed is 0.2h-1-3h-1(ii) a Preferably, the reaction temperature is 240-280 ℃, and/or the reaction pressure is 2.5-3.5 MPa, and/or the feeding volume space velocity is 0.5h-1-2h-1。
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