CN102335635B - Method for high-speed programmed temperature increase for reducing catalyst - Google Patents
Method for high-speed programmed temperature increase for reducing catalyst Download PDFInfo
- Publication number
- CN102335635B CN102335635B CN 201010228302 CN201010228302A CN102335635B CN 102335635 B CN102335635 B CN 102335635B CN 201010228302 CN201010228302 CN 201010228302 CN 201010228302 A CN201010228302 A CN 201010228302A CN 102335635 B CN102335635 B CN 102335635B
- Authority
- CN
- China
- Prior art keywords
- reduction
- catalyst
- hydrogen
- density
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 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 industrial production, and provides great scope of land for the mankind's activity in production.The finished catalyst majority that uses in the petrochemical production process belongs to supported solid catalyst, is comprised of carrier, auxiliary agent and active component three parts, and wherein the precursor of active component mostly is metallic salt.In commercial Application, most catalyst activity components only present metal atom state and load on the carrier and just can have preferably catalytic activity, 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 make metal oxide (oxidation state), 2) further with hydrogen metal oxide is reduced to metal simple-substance, a rear process is called the catalyst reduction process, the activation process that is called again catalyst, thus the catalyst finished product with catalytic active site just can be made.The catalytic activity of finished catalyst is except restricted standby factor affecting itself, and the revivification of catalyst process also is a very important factor, even can be called catalyst to the reduction of catalyst and prepare last one the most key step.The reduction effect quality of metal oxide plays decisive role to catalytic activity and the stability of finished catalyst in the catalyst, and then can have influence on quality and the output of product in the follow-up chemical process.
In the last few years, although along with the increase of catalizer variety and demand, man of most state inner catalyst processing factory is all built a catalyst reduction device, and because being subject to the impact of the 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 automatically adjusting 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 larger.Catalyst in reduction process, often because the active component of catalyst is violent in some or several temperature spot reduction reactions, 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 piecemeal temperature programming according to the prior temperature and time of predetermined section, if occur overtemperature in the reduction process or the temperature runaway phenomenon just takes to reduce the modes such as reducing gas air speed or minimizing heat supplement usually to prevent from burning out catalyst.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 affect catalyst overall activity and stable performance etc.Analysis is found, has the drawbacks such as catalyst reduction device ubiquity catalyst reduction time length and hydrogen gas consumption are large now, and this just causes the problems such as the whole process-cycle prolongation of catalyst and processing cost increase.
Summary of the invention
The problems such as long and hydrogen gas consumption is large for 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, in the situation that the catalyst reduction air speed is constant, utilizes the reduction control program to analyze entrance and exit density of hydrogen difference and adjust the reduction temperature of 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, the catalyst reduction time shorten can be 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 integral production cost.
Concrete technical scheme is as follows:
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, in the situation that guarantee that the catalyst reduction air speed is constant, the reduction control system changes the concentration of hydrogen in the reduction temperature of adjusting reduction furnace and the reducing gas 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 entrance 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 with 5～20 ℃/hour heating rate less than 2.0%, simultaneously the reduction furnace inlet gas is adjusted into hydrogen volume concentration and 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 density of hydrogen of reduction control system in inlet gas of 10～30min analysis and exit gas.
Preferably, described heating rate is 10～15 ℃/hour.
Preferably, the highest reduction temperature of described catalyst is 440 ℃.
In the present invention, if do not particularly point out, described 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, automatically regulates the reduction temperature of reduction furnace and the density of hydrogen in the reducing gas by variation tendency.
High-speed temperature programmed reducing catalyst process is minute three steps generally: the 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 as follows:
1, the reducing program starting stage
After the reduction control program starts, at first give the reduction variablees such as the reduction air speed of catalyst and heating rate, and the analysis result signal of identification 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 access is normal, and is ready to enter automatic control reduction phase.
2, the reduction furnace temperature programmed reduction stage
After entering the reduction control program, the reduction control program obtains the inlet gas of field assay instrument on-line analysis and the density of hydrogen in the exit gas every 5～30min, judge whether to need to adjust the reduction temperature of reduction furnace and the density of hydrogen in the reducing gas according to the two difference, realize the automatic control of reduction process, until whole reduction process finishes.
3, reduction furnace temperature programmed reduction termination phase
When the reduction control program monitored catalyst and reaches the highest reduction temperature, the cooling of program automatic alarm reduction apparatus entered the catalyst structure stage.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, such as the reduction of nickel-base catalyst, cobalt-base catalyst etc., be exemplified as particularly reduction for the synthesis of the nickel-base catalyst of isopropylamine, for the synthesis of the reduction of the cobalt-base catalyst of ethamine.
Catalyst reduction method of the present invention is compared with conventional method, have advantages of to save time and save hydrogen, because of the recovery time short so that the active component grain growth of catalyst is not obvious, catalyst granules is without powder phenomenon-tion.In addition, owing to having guaranteed the reducing gas air speed of catalyst in the catalyst reduction procedure of the present invention, even therefore occur overtemperature or the temperature runaway of bed in the reduction process, a large amount of gases also can in time shift out Heat of Formation, 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 is not subjected to 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 see Table 1.The density of hydrogen of every entrance of 30min analysis and exit gas.
The method concrete operations of high-speed temperature programmed reducing catalyst of the present invention are as follows: setting the reduction furnace rate of heat addition is 10 ℃/h, and the reduction air speed is 500h
-1Opening the reduction control program heats up, carry out simultaneously density of hydrogen in the on-line analysis reduction furnace entrance and exit gas every 10min, when furnace temperature rises to 220 ℃, on-line analysis detects the difference of density of hydrogen in the entrance and exit gas 〉=2.0%, then reducing program begins to keep furnace temperature, and reducing gas is switched to hydrogen volume concentration is 50% nitrogen and hydrogen mixture, the 0.5h post analysis, the density of hydrogen difference still 〉=2.0%, again density of hydrogen in the inlet gas is reduced to 40%, 0.5h post analysis, density of hydrogen difference＜2.0%, density of hydrogen is reverted to 50%, 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 is less than 2% the time in entrance and the exit gas, and the reduction control program begins slow intensification.When temperature rises to 350 ℃, on-line analysis detects the difference of density of hydrogen in the entrance and exit gas 〉=2.0%, 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, the difference of density of hydrogen＜2.0% reverts to 75% with density of hydrogen in the detection entrance and exit gas; Through behind the 0.5h, the difference of density of hydrogen is less than 2% in entrance and the exit gas, the reduction control program carries out heating reduction, the difference of density of hydrogen 〉=2.0% 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 ℃, the difference of density of hydrogen＜2.0% in on-line analysis detection discovery inlet gas and the exit gas, after keeping 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 finished.
The catalyst that gets with method of reducing of the present invention is designated as G-1.Be 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 sees Table 2 under the condition of 50ml.
Comparative Examples 1
Tradition used time of method of reducing and hydrogen gas consumption see Table 1.
The method concrete steps of tradition reducing catalyst are as follows: 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 then insulation 5h is warming up to 440 ℃ and be incubated 5h.The catalyst that gets with traditional method of reducing is designated as A-1.Be 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 sees 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 by data in the table 1, used total recovery time of method of the present invention is 75% of the tradition recovery time, and the hydrogen consumption total amount only is 73% of traditional reduction process.Found out by table 2 again, utilize the catalyst catalytic performance of method reduction of the present invention to be better than 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 (5)
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, in the situation that guarantee that catalyst reduction gas volume air speed is constant, the reduction control system changes at least one parameter in the density of hydrogen in the reduction temperature of adjusting reduction furnace and the reducing gas according to the difference of on-line analysis entrance and exit density of hydrogen; 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 gradually density of hydrogen in the reduction furnace inlet gas, until the initial concentration of hydrogen, if in the inlet gas in density of hydrogen and the exit gas difference of density of hydrogen then improve reduction temperature with 5～20 ℃/hour heating rate still less than 2.0%; When reduction temperature is adjusted to the highest reduction temperature of catalyst, kept reduction temperature 1～2 hour, the catalyst reduction process finishes.
2. the method for claim 1 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.
3. the method for claim 1 is characterized in that, the density of hydrogen of reduction control system in inlet gas of 10～30min analysis and exit gas.
4. the method for claim 1 is characterized in that, described heating rate is 10～15 ℃/hour.
5. method as claimed in claim 1 is characterized in that, the highest described reduction temperature is 440 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010228302 CN102335635B (en) | 2010-07-16 | 2010-07-16 | Method for high-speed programmed temperature increase for reducing catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010228302 CN102335635B (en) | 2010-07-16 | 2010-07-16 | Method for high-speed programmed temperature increase for reducing catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102335635A CN102335635A (en) | 2012-02-01 |
| CN102335635B true CN102335635B (en) | 2013-02-06 |
Family
ID=45511727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010228302 Active CN102335635B (en) | 2010-07-16 | 2010-07-16 | Method for high-speed programmed temperature increase for reducing catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102335635B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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 |
-
2010
- 2010-07-16 CN CN 201010228302 patent/CN102335635B/en active Active
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 (4)
| Title |
|---|
| CO低温变换催化剂的还原过程分析;张传玉;《安庆师范学院学报(自然科学版)》;20040229;第10卷(第01期);59-62 * |
| 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)》.2004,第10卷(第01期),59-62. |
| 杜鹃.甲醇催化剂快速升温还原的研究.《安徽化工》.2004,(第05期),44-45. |
| 甲醇催化剂快速升温还原的研究;杜鹃;《安徽化工》;20041231(第05期);44-45 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102335635A (en) | 2012-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102259003B (en) | Coke-oven gas methanation catalyst and preparation method thereof | |
| WO2016070805A1 (en) | Catalyst for selectively catalytically oxidizing hydrogen sulfide, catalyst for burning exhaust gas, and process for deeply catalytically oxidizing hydrogen sulfide to sulphur | |
| JP7037627B2 (en) | Control of exhaust gas incinerator | |
| CN104209115A (en) | Vanadium-series loading type high-temperature SCR catalyst and preparation method thereof | |
| CN102416327A (en) | Reduction method of copper zinc catalyst for hydrogen production by methanol steam reforming | |
| CN102335635B (en) | Method for high-speed programmed temperature increase for reducing catalyst | |
| CN113117712B (en) | Methane dry reforming reaction under microwave condition and catalyst thereof | |
| CN103170344B (en) | A kind of Catalysts and its preparation method for low temperature SCR denitration | |
| WO2014025274A1 (en) | Multicomponent oxide catalyst for low-temperature oxidation of methane and the method for preparation thereof | |
| US20220314166A1 (en) | Catalysts for NOx reduction and sulfur resistance | |
| Tong et al. | The effects of H2O and SO2 on the behaviour of CuSO4–CeO2/TS for low temperature catalytic reduction of NO with NH3 | |
| JP2019518927A5 (en) | ||
| CN104109092A (en) | Method for carbon monoxide gas phase synthesis of oxalate | |
| EA008455B1 (en) | Method for the high-temperature catalytic decomposition of no into nand o | |
| CN112105443B (en) | Method for reducing nitrogen dioxide in off-gas generated in olefin production process | |
| CN107744812B (en) | Preparation method of cobalt-manganese spinel double-wall microsphere catalyst | |
| Zhao et al. | Effects of CO2 on the low-temperature NH3-SCR performance of CeOx-biochar catalyst | |
| CN110508306A (en) | Biogas full constituent inverting biological catalyst for methanol LaNiO3/SiC-SiO2- Foam and preparation method thereof | |
| Zhihang et al. | Selective catalytic reduction of NOx with NH3 on a Cr-Mn mixed oxide at low temperature | |
| CN102335633B (en) | Rapid reducing method of catalyst | |
| Inayat et al. | Decomposition of N2O at low temperature over Co3O4 prepared by different methods | |
| Xie et al. | Selection of CO2 sorbent used in bio‐oil steam reforming process for hydrogen production | |
| CN102335634B (en) | Catalyst rapid reducing method | |
| CN112892569B (en) | Silicon carbide loaded cerium oxide catalyst and method for preparing sulfur by hydrogen sulfide selective oxidation under medium-high temperature condition by adopting same | |
| Ramos et al. | Diethyl Carbonate Production from CO2 and Ethanol in an Isothermal PFR via Aspen Plus Simulation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |