CN111420669A - Dry gas impurity removal catalyst for refinery plant - Google Patents
Dry gas impurity removal catalyst for refinery plant Download PDFInfo
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/864—Removing carbon monoxide or hydrocarbons
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a refinery dry gas impurity removal catalystAn agent comprising, in weight percent, Ni2O30.5-5% calculated as nickel oxide; 0.1-1% cobalt oxide calculated as CoO; with Cr2O30.01-0.3% of calculated chromium oxide; the balance of alumina carrier. The catalyst can simultaneously remove sulfur, arsenic, mercury, oxygen, oxynitride, alkyne and other impurities contained in refinery dry gas or pyrolysis gas, and has wide application prospect.
Description
Technical Field
The invention belongs to the fields of petrochemical industry and catalysis, relates to a refinery dry gas impurity removal catalyst, and particularly relates to a nickel-based catalyst for refinery dry gas impurity removal and a preparation method thereof.
Background
Refinery dry gas refers to non-condensed gas generated and recovered in oil refining process of oil refinery, also called distillation gas, mainly derived from secondary processing of crude oil, such as catalytic cracking (FCC), hydrocrackingDelayed coking, etc., wherein the amount of dry gas produced by catalytic cracking is maximized and the yield is maximized. The main component of refinery dry gas is H2、CO、CO2、O2、CH4、C2H4、C2H6、C3H8、C3H6And a small amount of C +4 compounds (heavy components), and further contains trace amounts of inorganic impurities such as sulfur, arsenic, mercury, oxygen, nitrogen oxides, and the like. The content of ethylene and ethane in the refinery dry gas is about 10-30%, and the content of hydrogen is about 20%. If these impurities can be removed by the catalyst, the recovery value of the olefin in the refinery dry gas can be remarkably improved.
The following important meanings are provided for recovering light hydrocarbon from refinery dry gas: A) the recovered light hydrocarbon can be sent to an ethylene separation system to recover ethylene, propylene and liquefied gas, and the recovered alkane can return to a cracking furnace, so that additional economic value is brought to a downstream ethylene or olefin device; B) the recovered ethylene can be reacted with benzene to produce ethylbenzene, which is used as a feedstock for the production of styrene. C) The recovered hydrogen can be sent to a refinery hydrogen network. D) The polypropylene comonomer ethylene can be provided to a fuel-type refinery polypropylene plant.
The process for recovering light hydrocarbon from refinery dry gas needs to jointly use a plurality of catalysts to respectively remove various impurities, for example, different catalysts are used to respectively remove oxygen, acetylene, methylacetylene, propadiene, arsenic, sulfur and the like, and the process gas components are relatively mixed, the content of various components is often not fixed, so that the surface carbon deposition of the conventional catalyst is easily increased, and the stability and the activity of the catalyst are reduced, which is the biggest problem for developing the catalyst.
Disclosure of Invention
In order to overcome the problems in the existing process for recovering light hydrocarbon from refinery dry gas, the inventor carries out deep research on a catalyst system in the process, focuses on improving the carbon deposition resistance, the carbon removal capability and the catalyst stability of the catalyst, and gives consideration to the removal of all impurities, thereby developing a nickel-based catalyst for the impurity removal of the refinery dry gas.
Specifically, the present invention includes the following technical solutions.
A refinery dry gas impurity removal catalyst is characterized by comprising the following components in percentage by weight:
a) with Ni2O3Calculated nickel oxide: 0.5 to 5 percent;
b) cobalt oxide as CoO: 0.1 to 1 percent;
c) with Cr2O3Calculated chromium oxide: 0.01 to 0.3 percent;
d) with Al2O3The alumina carrier is as follows: and (4) the balance.
The above nickel oxide is Ni2O3The content may be 0.5 to 4%, preferably 0.8 to 3.5%, more preferably 1.0 to 3%, more preferably 1 to 2%.
The content of the above cobalt oxide in terms of CoO may be 0.12 to 0.8%, preferably 0.13 to 0.7%, more preferably 0.14 to 0.6%, still more preferably 0.15 to 0.5%.
The chromium oxide is Cr2O3The content may be 0.02 to 0.25%, preferably 0.03 to 0.23%, more preferably 0.04 to 0.2%, more preferably 0.05 to 0.15%.
The alumina carrier material may be selected from calcined α -alumina, gamma-alumina, high purity alumina, and activated alumina.
The invention also provides a method for preparing the refinery dry gas impurity removal catalyst, wherein the catalyst is prepared by adopting an impregnation method and specifically comprises the following steps:
1) weighing raw materials of each component according to a ratio, preparing a metal salt solution by using deionized water, and uniformly mixing;
2) immersing alumina carrier particles in the above metal salt solution for 0.5 to 5 hours, for example, 1 to 2 hours;
3) washing the impregnated particles with deionized water, separating, and drying;
4) the particles obtained in step 3) are dried at 100-150 ℃, e.g. 120-130 ℃, for 1-5 hours, e.g. 2-3 hours, at 200-250 ℃, e.g. 220-240 ℃, for 0.5-3 hours, e.g. 1-2 hours, and at 500-1000 ℃, e.g. 700-800 ℃, for 2-8 hours, e.g. 4-6 hours, to obtain the catalyst.
In the method, the nickel oxide raw material can be nickel nitrate, the cobalt oxide raw material can be cobalt nitrate, and the chromium oxide raw material can be chromium nitrate.
Preferably, at least one pore-forming agent can be further added in the step 2), and the dosage of the pore-forming agent is 1-10% of the weight of the catalyst. The pore-forming agent can be selected from graphite, polystyrene microspheres and carboxymethyl cellulose.
The diameter of the sphere in the above step 3) is preferably 6 to 8 mm.
The invention also provides the application of the refinery dry gas impurity removal catalyst in the refinery dry gas impurity removal or pyrolysis gas.
The nickel-based catalyst has a comprehensive impurity removal function, can simultaneously remove impurities such as sulfur, arsenic, mercury, oxygen, oxynitride, alkyne and the like in refinery dry gas or pyrolysis gas, reduces the loss of olefin, and controls the loss of olefin within 1 percent, thereby having wide application prospect.
Detailed Description
For convenience of description, the "refinery dry gas removal catalyst" of the present invention is sometimes referred to herein simply as "refinery dry gas catalyst", "nickel-based catalyst" or "catalyst".
The nickel-based catalyst is used for simultaneously removing inorganic impurities such as sulfur, arsenic, mercury, oxygen, oxynitride and the like and organic impurities such as alkyne and the like in refinery dry gas. When refinery dry gas is treated by the nickel-based catalyst, inorganic impurities such as sulfur, arsenic, mercury, oxygen and nitrogen oxides can react as follows:
H2s participates in the sulfuration of the catalyst, so that the catalyst is changed into a nickel sulfide state;
heavy metals of mercury and arsenic are adsorbed by the catalyst;
NOX+H2→NH3+H2o, wherein NOXRepresents one or more nitrogen oxides;
O2+H2→H2O。
organic impurities alkynes undergo the following reactions:
the acetylene is mostly converted to ethylene: CH ≡ CH + H2→CH2=CH2;
The hydrogenation of methylacetylene and propadiene to produce propylene. CH (CH)3CH≡CH+H2→CH3CH=CH2;
CH2=C=CH2+H2→CH3CH=CH2。
The ethylene and the propylene are needed by users and can be used for synthesizing different products in the downstream.
In preparing the nickel-based catalyst, the nickel oxide raw material may be selected from nickel salts such as nickel nitrate, nickel carbonate, nickel hydrochloride, nickel sulfate, nickel oxide, nickel protoxide, nickel tetraoxide, or a mixture of two or more thereof, preferably nickel nitrate. Nickel oxide with Ni2O3The content is 0.5-5%, preferably about 1.0-2.0%.
It should be understood that when numerical features are expressed herein, the terms "about" or "approximately" mean that the number indicated may have a margin of error or variance of 10%, ± 9%, ± 8%, ± 7%, ± 6% or ± 5%.
When the content of nickel oxide is lower than 0.5%, the catalytic activity of the catalyst is remarkably reduced, and impurities in the refinery dry gas are difficult to be catalyzed to fully react so as to remove the impurities; when the content of nickel oxide is more than 5%, the balance effect of remarkably improving the catalytic activity cannot be obtained, and the production cost of the catalyst is increased, and the loss rate of olefin is increased, resulting in a serious decrease in economical efficiency.
The catalytic activity or catalytic active body of the catalyst can be represented by indexes such as ethylene loss rate, acetylene conversion rate, methyl acetylene conversion rate, propadiene conversion rate, oxygen conversion rate and the like of refinery dry gas.
The cobalt oxide starting material may be selected from cobalt salts such as cobalt nitrate, cobalt carbonate, cobalt hydrochloride, cobalt sulfate, CoO, Co3O4、CoO2Or a mixture of two or more thereof, preferably cobalt nitrate. The cobalt oxide content, calculated as CoO, is 0.1-1%, preferably about 0.15-0.20%.
When the cobalt oxide content is less than 0.1%, the ethylene loss rate is high, resulting in a reduction in product economy; when the cobalt oxide content is more than 1%, a balance effect of remarkably improving the catalytic activity cannot be obtained, and the production cost of the catalyst is increased.
The chromium oxide raw material may be selected from chromium salts such as chromium nitrate, chromium carbonate, chromium hydrochloride, chromium sulfate, chromia (CrO), chromium oxide (Cr)2O3) Chromium trioxide (CrO)3) Chromium dioxide (CrO)2) Or a mixture of two or more thereof, preferably chromium nitrate. Chromium oxide with Cr2O3The content is 0.01-0.3%, preferably about 0.05-0.10%.
When the chromium oxide content is less than 0.01%, the ethylene loss rate is high, resulting in a decrease in product economy; when the content of chromium oxide is more than 0.3%, the balance effect of remarkably improving the catalytic activity cannot be obtained and the production cost of the catalyst is increased.
In order to realize the maximum distribution uniformity of the nickel oxide, the cobalt oxide and the chromium oxide in the catalyst, the raw materials of the components can be mixed by a wet method, that is, the water-soluble raw materials of the nickel oxide, the cobalt oxide and the chromium oxide are firstly dissolved in water (such as deionized water) to prepare a metal salt solution, and then the alumina serving as a catalyst carrier is soaked in the metal salt solution, so that the raw materials of the components are mixed, namely the step 1 is completed.
Nickel nitrate, cobalt nitrate and chromium nitrate are all water-soluble metal salts that can be conveniently used for the above-mentioned wet mixing.
In order that the invention may be more readily understood, preferred embodiments will now be described in detail. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and are not intended to limit the present invention.
Examples
The addition amount, the content and the concentration of various substances are referred to in the examples, wherein the parts are all referred to as weight parts unless otherwise specified; the percentages are by weight unless otherwise indicated.
In the examples, if no specific description is made about the experimental operating temperature, the temperature is usually room temperature (10-30 ℃).
In the examples, the concentration/content of acetylene, methylacetylene, propadiene, butadiene and their conversion products such as ethylene and the like, which are organic impurities, was measured by gas chromatography.
The chromatographic type is as follows: shimadzu GC-2014
A detector: FID
A chromatographic column: al2O3 capillary column
Carrier gas: n2
The split ratio is as follows: 50
Sample inlet temperature: 300 deg.C
Column temperature: 50 deg.C
Detector temperature: at 250 ℃ to obtain a mixture.
Example 1
100.0 g of spherical alumina having a diameter of 8 to 9 mm was immersed in a metal salt solution containing 2.0% nickel nitrate, 0.26% cobalt nitrate and 0.10% chromium nitrate. After dipping for 1 hour, adding deionized water for washing, drying for 2 hours at 120 ℃, drying for 0.5 hour at 230 ℃, then placing in a muffle furnace, and roasting for 4 hours at 800 ℃ to obtain the catalyst, wherein the contents of the components are listed in Table 1.
The activity evaluation of the prepared catalyst is carried out in an isothermal fixed bed, and the specific process comprises the following steps: cracking gas with prepared components as required is used for simulating refinery dry gas, the cracking gas is input into a preheating mixer through a metering pump and enters a reactor, the reactor is a 1-inch stainless steel pipe and can be filled with 50ml of catalyst, the reactor is heated to the temperature required by reaction by adopting an electric heating wire, reactants flowing out of the reactor are analyzed for components by using gas chromatography, and the loss rate of ethylene, the conversion rate of acetylene, the conversion rate of methyl acetylene, the conversion rate of propadiene and the conversion rate of oxygen are calculated by adopting the following formulas:
ethylene loss rate ═ inlet ethylene content-outlet ethylene content)/inlet ethylene content × 100%;
acetylene conversion (% acetylene inlet content-acetylene outlet content)/acetylene inlet content × 100%;
conversion of methylacetylene% (% conversion of inlet methylacetylene-outlet methylacetylene)/inlet methylacetylene content × 100%;
allene conversion% (% inlet allene content-outlet allene content)/inlet allene content × 100%;
oxygen conversion% (% inlet oxygen content-outlet oxygen content)/inlet oxygen content × 100%.
The cracking gas prepared in the experiment consists of: h2,25%;O2,0.5%;C2H2,0.5%;C2H6,5%,C3H8,0.05%,C2H426%; methylacetylene (C)3H4) 0.09%; propadiene (C)3H4)0.07%。
50ml of catalyst is loaded into a reactor, and the pressure of cracking gas is 1.7MPa, and the space velocity is 3000 hours-1The catalytic activity was evaluated at 205 ℃ and the test results are shown in Table 2.
Example 2
A catalyst was prepared by following the procedure of example 1 except that the metal salt solution contained 3.3% nickel nitrate, 0.26% cobalt nitrate, and 0.10% chromium nitrate, and the contents of the components of the prepared catalyst are shown in Table 1. After the catalyst was prepared, the activity of the catalyst was evaluated according to the evaluation method of example 1, and the test results are shown in Table 2.
Example 3
A catalyst was prepared by following the procedure of example 1 except that the metal salt solution contained 3.3% nickel nitrate, 0.40% cobalt nitrate, and 0.20% chromium nitrate, and the contents of the components of the prepared catalyst are shown in Table 1. After the catalyst was prepared, the activity of the catalyst was evaluated according to the evaluation method of example 1, and the test results are shown in Table 2.
TABLE 1 composition of catalyst of each of the above examples
TABLE 2 examination of catalytic Activity of examples
Example 1
On-line time h | 60 | 72 | 100 | 200 | 250 |
Reaction temperature | 220 | 227 | 220 | 227 | 240 |
Ethylene loss% | 0.8 | 1.1 | 1.2 | 1.8 | 2.0 |
Conversion of acetylene% | 95.7 | 100 | 99 | 93 | 98 |
Conversion of methylacetylene% | 66 | 80 | 73 | 77 | 82 |
Allene conversion% | 48 | 51 | 47 | 53 | 65 |
Oxygen conversion% | 100 | 100 | 100 | 100 | 100 |
Example 2
On-line time h | 60 | 72 | 100 | 200 | 250 |
Reaction temperature | 220 | 227 | 220 | 227 | 240 |
Ethylene loss% | 0.9 | 1.3 | 1.2 | 1.9 | 2.5 |
Conversion of acetylene% | 96.8 | 100 | 99 | 100 | 99 |
Conversion of methylacetylene% | 69 | 79 | 75 | 78 | 83 |
Allene conversion% | 43 | 53 | 54 | 55 | 62 |
Oxygen conversion% | 100 | 100 | 100 | 100 | 100 |
Example 3
The above experiments show that the catalysts of examples 1-3 are both effective in removing oxygen; the loss rate of ethylene is low and is not higher than 2.5%; can effectively promote the conversion of organic impurities of acetylene, methylacetylene and propadiene, and achieve the purpose of impurity removal and purification.
Comparative example 1
A catalyst was prepared by the method of example 1 except that nickel nitrate, cobalt nitrate, and chromium nitrate in the metal salt solution were adjusted so that the content of nickel oxide was 0.4%, and the contents of the components of the prepared catalyst were as shown in table 3. After the catalyst was prepared, the activity of the catalyst was evaluated according to the evaluation method of example 1, and the test results are shown in Table 4.
Comparative example 2
A catalyst was prepared as in example 1, except that nickel nitrate, cobalt nitrate and chromium nitrate in the metal salt solution were adjusted so that the cobalt oxide content was 0.075%, and the catalyst components were as shown in Table 3. After the catalyst was prepared, the activity of the catalyst was evaluated according to the evaluation method of example 1, and the test results are shown in Table 4.
Comparative example 3
A catalyst was prepared by following the procedure of example 1 except that nickel nitrate, cobalt nitrate and chromium nitrate in the metal salt solution were adjusted so that the content of chromium oxide was 0.005%, and the contents of the respective components of the prepared catalyst were as shown in table 3. After the catalyst was prepared, the activity of the catalyst was evaluated according to the evaluation method of example 1, and the test results are shown in Table 4.
TABLE 3 compositions of the above comparative catalysts
Composition of | Comparative example 1 | Comparative example 2 | Comparative example 3 |
Ni2O3 | 0.40% | 2.00% | 2.00% |
CoO | 0.15% | 0.075% | 0.20% |
Cr2O3 | 0.05% | 0.05% | 0.005% |
Alumina oxide | 99.40% | 97.875% | 97.795% |
TABLE 4 catalytic Activity investigation of the respective comparative examples
Comparative example 1
Comparative example 2
On-line time h | 60 | 72 | 100 | 200 | 250 |
Reaction temperature | 220 | 227 | 220 | 227 | 240 |
Ethylene loss% | 1.1 | 1.5 | 1.8 | 2.0 | 3.0 |
Conversion of acetylene% | 100 | 93 | 98 | 99 | 99 |
Conversion of methylacetylene% | 69 | 77 | 78 | 79 | 86 |
Allene conversion% | 43 | 52 | 52 | 56 | 69 |
Oxygen conversion% | 100 | 100 | 100 | 100 | 100 |
Comparative example 3
On-line time h | 60 | 72 | 100 | 200 | 250 |
Reaction temperature | 220 | 227 | 220 | 227 | 240 |
Ethylene loss% | 1.3 | 1.3 | 1.5 | 2.4 | 3.5 |
Conversion of acetylene% | 100 | 100 | 100 | 100 | 99 |
Conversion of methylacetylene% | 65 | 75 | 76 | 76 | 82 |
Allene conversion% | 49 | 51 | 53 | 55 | 69 |
Oxygen conversion% | 100 | 100 | 100 | 100 | 100 |
The above experiments show that when the nickel (Ni) content is less than 0.5%, the catalyst activity is low and it is difficult to effectively remove oxygen; when the Co and Cr are lower than the value, the ethylene loss rate is higher and can reach 3.5 percent at most, so that the product economy is reduced.
Although the technical solution of the present invention has been described above by taking artificially prepared pyrolysis gas as an example and simulating refinery dry gas, it will be obvious to those skilled in the art that the technical solution of the present invention is also applicable to other similar catalysts, such as catalysts with added binder, catalysts with inert carriers other than alumina, according to the disclosure of the present invention. Therefore, without departing from the spirit of the invention, those skilled in the art can make various changes or modifications to the invention, and equivalents of the various changes or modifications should also fall within the scope of the invention.
Claims (10)
1. A refinery dry gas impurity removal catalyst is characterized by comprising the following components in percentage by weight:
a) with Ni2O3Calculated nickel oxide: 0.5 to 5 percent;
b) cobalt oxide as CoO: 0.1 to 1 percent;
c) with Cr2O3Calculated chromium oxide: 0.01 to 0.3 percent;
d) with Al2O3The alumina carrier is as follows: and (4) the balance.
2. The refinery dry gas impurity removal catalyst of claim 1, wherein the nickel oxide is Ni2O3The content is 0.5-4%.
3. The catalyst for the removal of impurities from refinery dry gas according to claim 1, wherein the cobalt oxide is contained in an amount of 0.12-0.8% in terms of CoO.
4. The refinery dry gas impurity removal catalyst of claim 1, wherein the chromium oxide is Cr2O3The content is 0.02-0.25%.
5. The refinery dry gas impurity removal catalyst of claim 1, wherein the alumina support material is selected from calcined α -alumina, high purity alumina, activated alumina.
6. The refinery dry gas impurity removal catalyst of claim 1, wherein the nickel oxide is Ni2O31.0-2.0% of cobalt oxide, 0.15-0.20% of cobalt oxide, and Cr oxide, wherein the Cr oxide is Cr2O3The content is 0.05-0.10%.
7. A method for preparing the refinery dry gas impurity removal catalyst according to any one of claims 1-6, comprising the steps of:
1) weighing raw materials of each component according to a ratio, preparing a metal salt solution by using deionized water, and uniformly mixing;
2) dipping the alumina carrier particles in a metal salt solution for 0.5-5 hours;
3) washing the impregnated particles with deionized water, separating, and drying;
4) drying the particles obtained in the step 3) at the temperature of 100-150 ℃ for 1-5 hours, drying at the temperature of 200-250 ℃ for 0.5-3 hours, and roasting at the temperature of 500-1000 ℃ for 2-8 hours to obtain the catalyst.
8. The method of claim 7, wherein the nickel oxide feedstock is nickel nitrate, the cobalt oxide feedstock is cobalt nitrate, and the chromium oxide feedstock is chromium nitrate.
9. The method as claimed in claim 7, wherein at least one pore-forming agent selected from graphite, polystyrene microspheres, and carboxymethyl cellulose is further added in step 2), and the amount of the pore-forming agent is 1-10% by weight of the catalyst.
10. Use of the refinery dry gas impurity removal catalyst according to any one of claims 1-6 in the impurity removal of refinery dry gas or pyrolysis gas.
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