CN102335635A - High-speed temperature programmed reduction method for catalyst - Google Patents
High-speed temperature programmed reduction method for catalyst Download PDFInfo
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- CN102335635A CN102335635A CN2010102283026A CN201010228302A CN102335635A CN 102335635 A CN102335635 A CN 102335635A CN 2010102283026 A CN2010102283026 A CN 2010102283026A CN 201010228302 A CN201010228302 A CN 201010228302A CN 102335635 A CN102335635 A CN 102335635A
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Abstract
The invention relates to a high-speed temperature programmed reduction method for a catalyst. In order to solve the universal problems of long catalyst reduction time and great hydrogen consumption in present catalyst reduction equipment, the inventor puts forward the method of: during a catalyst reduction process, conducting on-line analysis for hydrogen concentrations in the inlet gas and outlet gas of a reduction furnace, and under a constant catalyst reduction space velocity, analyzing the difference of hydrogen concentrations at the inlet and outlet by a reduction control program, and adjusting the reduction temperature in the reduction furnace as well as the hydrogen concentration in the reduction gas. The method of the invention can guarantee the reduction of overall catalyst reduction time and the saving of hydrogen consumption based on fully reducing the catalyst, so that the overall processing period of the catalyst is substantially shortened and the catalyst production cost is reduced, thus boasting extensive practical application value.
Description
Technical field
The present invention relates to a kind of catalyst reduction method, more particularly, relate to a kind of method that is used for the high-speed temperature programmed reducing catalyst.
Background technology
Modern age chemical engineering industry, particularly coal and petrochemical industry develop rapidly, thousands of chemical raw materials and commodity production are all closely related with the exploitation of industrial catalyst.The existence of catalyst has not only promoted the technological innovation in the commercial production, and is that human activity in production provides great scope of land.The finished catalyst majority that uses in the petrochemical production process belongs to the supported solid catalyst, is made up of carrier, auxiliary agent and active component three parts, and wherein mostly the precursor of active component is metallic salt.In commercial Application; Most catalyst activity components only present metal atom state and load on the carrier and just can have catalytic activity preferably; Therefore; The forming process of supported solid catalyst can be divided into following two processes: 1) must will load on metal component on the carrier and carry out pyrolytic and process metal oxide (oxidation state), 2) further metal oxide is reduced to metal simple-substance with hydrogen, back one process is called the catalyst reduction process; The activation process that is called catalyst again, thus catalyst finished product just can be processed with catalytic active site.The catalytic activity of finished catalyst is except the factor affecting that receives preparation itself, and the catalyzer temperature-elevating reduction process also is a very important factor, even can be called the last one the most key step of Preparation of Catalyst to the reduction of catalyst.The reduction effect quality of metal oxide plays decisive role to the catalytic activity and the stability of finished catalyst in the catalyst, and then can have influence on the quality and the output of product in the follow-up chemical process.
In the last few years, though along with the increase of catalizer variety and demand, the catalyst reduction device had all been had in man of most state inner catalyst processing factory, and because of receiving the influence of many factors such as process conditions, unit scale is uneven, and catalytic reduction effect quality differs.These devices mostly adopt the temperature-programmed technique means; The nitrogen and hydrogen mixture that contains high concentration hydrogen (wherein hydrogen volume content is 72%～74%) that uses ammonia decomposition device production as reducing gas manually or self-checking device go back the raw parameter reducing catalyst; The most directly emptying of reducing gas tail gas; One furnace catalyst recovery time reached 60～70h, and hydrogen gas consumption is bigger.Catalyst in reduction process, often since the activity of such catalysts component some or several temperature point reduction reaction is violent, a large amount of reaction heat that discharge and can not in time withdraw overtemperature or the temperature runaway that just forms beds.And the temperature of existing catalyst reduction device control mostly is to carry out temperature programming piecemeal according to the temperature and time of predetermined section in advance, just takes to reduce the reducing gas air speed usually and perhaps reduces mode such as heat supplement to prevent to burn out catalyst if occur overtemperature or temperature runaway phenomenon in the reduction process.But the reduction of reducing gas air speed also just means the reduction of hydrogen linear velocity, is to cause air-flow bias current or channel on the one hand, the beds excessive temperature differentials, and catalyst reduction is inhomogeneous; Be that the heat that overtemperature or temperature runaway discharge can not in time be taken away on the other hand, temperature can not reduce very soon, overstand, and long-time high temperature then can cause sintering of catalyst, thereby influence catalyst overall activity and stable performance etc.Analysis is found, has drawbacks such as catalyst reduction device ubiquity catalyst reduction time length and hydrogen gas consumption are big now, and this just causes problems such as whole process-cycle prolongation of catalyst and processing cost increase.
Summary of the invention
Problems such as long and hydrogen gas consumption is big to the current catalyst reduction device ubiquitous catalyst reduction time; The inventor is on the basis of existing operation; Density of hydrogen in on-line analysis reduction furnace inlet gas and the exit gas; Under the constant situation of catalyst reduction air speed, utilize the reduction control program to analyze the reduction temperature of entrance and exit density of hydrogen difference adjustment reduction furnace and the density of hydrogen in the reducing gas.Result of the test is found, uses the method for high-speed temperature programmed reducing catalyst of the present invention, can the catalyst reduction time be shortened to 80%～90% of existing method of reducing, and hydrogen gas consumption also declines to a great extent.This has not only shortened catalyst whole process time, has improved the annual production of reduction furnace, and has reduced catalyst production cost.
Concrete technical scheme is following:
The method of catalyst fast restore of the present invention; In the catalyst reduction process; Density of hydrogen in on-line analysis reduction furnace inlet gas and the exit gas; Analysis result is written in the catalyst reduction control system, is guaranteeing under the constant situation of catalyst reduction air speed, reduction control system changes the concentration of hydrogen in reduction temperature and the reducing gas of adjustment reduction furnace according to the difference of on-line analysis entrance and exit density of hydrogen.
Preferably; If the difference of density of hydrogen >=2.0% in density of hydrogen and the exit gas in the reduction furnace inlet gas; Then keep reduction temperature constant, in reduction furnace inlet nitrogen and hydrogen mixture, replenish simultaneously nitrogen hydrogen volume concentration is adjusted into 10%～30% and to keep the catalyst reduction air speed constant by 75%; If in the inlet gas in density of hydrogen and the exit gas difference of density of hydrogen then improve reduction temperature less than 2.0% with 5～20 ℃/hour heating rate, simultaneously the reduction furnace inlet gas being adjusted into hydrogen volume concentration is 75% nitrogen and hydrogen mixture; When reduction temperature is adjusted to the highest reduction temperature of catalyst, kept reduction temperature 1～2 hour, the catalyst reduction process finishes.
Preferably, the initial volume air speed of catalyst reduction gas is 1.0～10000.0h
-1, density of hydrogen is 75% in the reducing gas.
Preferably, the every density of hydrogen in inlet gas of 10～30min analysis and exit gas of reduction control system.
Preferably, described heating rate is 10～15 ℃/hour.
Preferably, the highest reduction temperature of said catalyst is 440 ℃.
In the present invention, if do not particularly point out, said concentration all refers to volume percent content.
In high-speed temperature programmed method of reducing of the present invention, the foundation that the reduction control program is regulated is the variation of density of hydrogen in reduction furnace inlet gas and the exit gas.The reduction control program calculates the two difference according to the on-line analysis result of density of hydrogen in the reduction furnace entrance and exit gas, regulates the reduction temperature of reduction furnace and the density of hydrogen in the reducing gas automatically by variation tendency.
Three steps of the general branch of high-speed temperature programmed reducing catalyst process: reduction control program starting stage; The reduction furnace temperature programmed reduction stage; Reduction furnace temperature programmed reduction termination phase.The idiographic flow of high-speed temperature programmed reduction catalysts agent method is following:
1, the reducing program starting stage
After the reduction control program starts, reduction variablees such as the reduction air speed of at first giving catalyst and heating rate, and discern the analysis result signal of reduction furnace entrance and exit online analytical instrument.
Confirm that all execute-in-places all are finished, on-the-spot on-line analysis device data inserts normal, and is ready to get into automatic control reduction phase.
2, the reduction furnace temperature programmed reduction stage
After getting into the reduction control program; The reduction control program whenever obtains the inlet gas of field assay instrument on-line analysis and the density of hydrogen in the exit gas at a distance from 5～30min; Need to judge whether the reduction temperature of adjustment reduction furnace and the density of hydrogen in the reducing gas according to the two difference; Realize the automatic control of reduction process, finish until whole reduction process.
3, reduction furnace temperature programmed reduction termination phase
When the reduction control program monitors catalyst when reaching the highest reduction temperature, program reminds the reduction apparatus cooling to get into the catalyst structure stage automatically.Manually stop reducing control program by operating personnel.
The method of high-speed temperature programmed reducing catalyst of the present invention can be used for the reduction of various catalyst; The for example reduction of nickel-base catalyst, cobalt-base catalyst etc., be exemplified as particularly the nickel-base catalyst that is used for synthesizing isopropamide reduction, be used for the reduction of the cobalt-base catalyst of synthetic ethamine.
Catalyst reduction method of the present invention is compared with conventional method, has the advantage of saving time and saving hydrogen, makes that because of the recovery time is short activity of such catalysts component grain growth is not obvious, and catalyst granules does not have powder phenomenon-tion.In addition; Owing to guaranteed the reducing gas air speed of catalyst in the catalyst reduction procedure of the present invention; Even therefore occur the overtemperature or the temperature runaway of bed in the reduction process, a large amount of gases also can in time shift out generating heat, are unlikely to catalyst activity component sintering.
The specific embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention does not receive the restriction of following embodiment.
Embodiment 1
Method of the present invention is applied to the nickel-base catalyst reduction process.The nickel-base catalyst loadings is 1.0m
3, heating rate is 10 ℃/h, the reduction air speed is 500h
-1, density of hydrogen is 75% in the reducing gas, used time of method of reducing of the present invention and hydrogen gas consumption are seen table 1.Every 30min analyzes once the density of hydrogen of inlet and exit gas.
The method concrete operations of high-speed temperature programmed reducing catalyst of the present invention are following: setting the reduction furnace rate of heat addition is 10 ℃/h, and the reduction air speed is 500h
-1, opening the reduction control program and heat up, every separated 10min carries out the density of hydrogen in the on-line analysis reduction furnace entrance and exit gas simultaneously, when furnace temperature rises to 220 ℃; On-line analysis detects difference>=2.0% of density of hydrogen in the entrance and exit gas, and then reducing program begins to keep furnace temperature, and reducing gas is switched to hydrogen volume concentration is 50% nitrogen and hydrogen mixture; 0.5h post analysis, density of hydrogen difference are still>=2.0%, again density of hydrogen in the inlet gas reduced to 40%; 0.5h post analysis, density of hydrogen difference＜2.0% reverts to 50% with density of hydrogen; Through 0.5h, analyze and learn density of hydrogen difference＜2.0% again, density of hydrogen is reverted to 75%; Through the 0.5h post analysis, the difference of density of hydrogen was less than 2% o'clock in inlet and the exit gas, and the reduction control program begins slow intensification.When temperature rises to 350 ℃; On-line analysis detects difference >=2.0% of density of hydrogen in the entrance and exit gas; Then reducing program begins to keep furnace temperature, and reducing gas is switched to hydrogen volume concentration is 50% nitrogen and hydrogen mixture, through behind the 0.5h; Detect difference＜2.0% of density of hydrogen in the entrance and exit gas, density of hydrogen is reverted to 75%; Through behind the 0.5h; The difference of density of hydrogen is less than 2% in inlet and the exit gas, and the reduction control program carries out heating reduction, difference >=2.0% of density of hydrogen in the analyzing and testing entrance and exit gas when being warming up to 390 ℃; Then reducing program begins to keep furnace temperature; And reducing gas is switched to hydrogen volume concentration is 50% nitrogen and hydrogen mixture, detects behind the insulation 0.5h and learns concentration difference＜2.0%, and density of hydrogen is reverted to 75%; Detect behind the insulation 0.5h and learn concentration difference＜2.0%; Reducing program continues to heat up 440 ℃, and on-line analysis detects difference＜2.0% of finding density of hydrogen in inlet gas and the exit gas, behind the maintenance reduction 1h; Basicly stable 0.1%～0.2%; 440 ℃ of maximum temperatures that reach catalyst of furnace temperature, reducing program stops, and the whole reduction process of catalyst is accomplished.
The catalyst that gets with method of reducing of the present invention is designated as G-1.Is 0.5h through the catalyst G-1 of reduction at 150 ℃, the volume space velocity of acetone
-1, acetone: hydrogen: the mol ratio of ammonia is that 1: 3: 3, catalyst amount are that evaluation result is seen table 2 under the condition of 50ml.
Comparative Examples 1
Tradition used time of method of reducing and hydrogen gas consumption are seen table 1.
The method concrete steps of tradition reducing catalyst are following: the nickel-base catalyst loadings is 1.0m
3, heating rate is 10 ℃/h, the air speed of reducing gas is 500h
-1, density of hydrogen is 75%.The room temperature start program is warming up to 220 ℃, and reduction furnace is warming up to 340 ℃ behind the insulation 6h, and 340 ℃ of insulations are warming up to 400 ℃ behind the 5h, and insulation 5h is warming up to 440 ℃ and be incubated 5h then.The catalyst that gets with traditional method of reducing is designated as A-1.Is 0.5h through the catalyst A-1 of reduction at 150 ℃, the volume space velocity of acetone
-1, acetone: hydrogen: ammonia is that 1: 3: 3, catalyst amount are that evaluation result is seen table 2 under the condition of 50ml.
The table 1 catalyst reduction step table of comparisons
Table 2 evaluating catalyst result contrast
Can be found out that by data in the table 1 used total recovery time of method of the present invention is 75% of the tradition recovery time, the hydrogen consumption total amount is merely 73% of traditional reduction process.Find out by table 2 again, utilize the catalyst catalytic performance of method reduction of the present invention to be superior to existing method of reducing.Therefore, high-speed temperature programmed method of reducing of the present invention has reduced hydrogen gas consumption guaranteeing not only to have shortened the recovery time of catalyst on the basis that catalyst fully reduces, and greatly reduces the reduction cost of catalyst.
Claims (6)
1. the method for a high-speed temperature programmed reducing catalyst; It is characterized in that; In catalyst temperature programmed reduction process; Density of hydrogen in on-line analysis reduction furnace inlet gas and the exit gas; Analysis result is written in the catalyst reduction control system, is guaranteeing under the constant situation of catalyst reduction gas volume air speed, reduction control system changes at least one parameter in the density of hydrogen in reduction temperature and the reducing gas of adjustment reduction furnace according to the difference of on-line analysis entrance and exit density of hydrogen.
2. the method for claim 1; It is characterized in that; If the difference of density of hydrogen >=2.0% in density of hydrogen and the exit gas in the reduction furnace inlet gas then keeps reduction temperature constant, the density of hydrogen of reduction furnace inlet gas is reduced to 50%～90% of former hydrogen concentration; If in the inlet gas in density of hydrogen and the exit gas difference of density of hydrogen less than 2.0%; Then improve density of hydrogen in the reduction furnace inlet gas gradually; Initial concentration until hydrogen; If in the inlet gas in density of hydrogen and the exit gas difference of density of hydrogen then improve reduction temperature still less than 2.0% with 5～20 ℃/hour heating rate; When reduction temperature is adjusted to the highest reduction temperature of catalyst, kept reduction temperature 1～2 hour, the catalyst reduction process finishes.
3. according to claim 1 or claim 2 method is characterized in that the initial volume air speed of catalyst reduction gas is 1.0～10000.0h
-1, density of hydrogen is 75% in the reducing gas.
4. according to claim 1 or claim 2 method is characterized in that, the every density of hydrogen in inlet gas of 10～30min analysis and exit gas of reduction control system.
5. method as claimed in claim 2 is characterized in that, described heating rate is 10～15 ℃/hour.
6. method as claimed in claim 2 is characterized in that the highest said reduction temperature is 440 ℃.
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| CN 201010228302 CN102335635B (en) | 2010-07-16 | 2010-07-16 | Method for high-speed programmed temperature increase for reducing catalyst |
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| CN 201010228302 CN102335635B (en) | 2010-07-16 | 2010-07-16 | Method for high-speed programmed temperature increase for reducing catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977843A (en) * | 2014-05-27 | 2014-08-13 | 山西兰花科技创业股份有限公司 | Methanol catalyst temperature-rising reduction method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827218A (en) * | 2006-03-30 | 2006-09-06 | 上海工程技术大学 | Method for preparing supported nano copper nickel catalyst and application thereof in oxidative dehydrogenation reaction of alkylol amine |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1827218A (en) * | 2006-03-30 | 2006-09-06 | 上海工程技术大学 | Method for preparing supported nano copper nickel catalyst and application thereof in oxidative dehydrogenation reaction of alkylol amine |
Non-Patent Citations (2)
| Title |
|---|
| 张传玉: "CO低温变换催化剂的还原过程分析", 《安庆师范学院学报(自然科学版)》, vol. 10, no. 01, 29 February 2004 (2004-02-29), pages 59 - 62 * |
| 杜鹃: "甲醇催化剂快速升温还原的研究", 《安徽化工》, no. 05, 31 December 2004 (2004-12-31), pages 44 - 45 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103977843A (en) * | 2014-05-27 | 2014-08-13 | 山西兰花科技创业股份有限公司 | Methanol catalyst temperature-rising reduction method |
| CN103977843B (en) * | 2014-05-27 | 2016-01-20 | 山西兰花科技创业股份有限公司 | A kind of method of methyl alcohol catalyst heating reduction |
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