CN102335634B - Catalyst rapid reducing method - Google Patents
Catalyst rapid reducing method Download PDFInfo
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- CN102335634B CN102335634B CN 201010228301 CN201010228301A CN102335634B CN 102335634 B CN102335634 B CN 102335634B CN 201010228301 CN201010228301 CN 201010228301 CN 201010228301 A CN201010228301 A CN 201010228301A CN 102335634 B CN102335634 B CN 102335634B
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Abstract
The invention relates to a catalyst rapid reducing method. According to the method, with a reducing furnace reduction controlling program, a hydrogen flow and a heating rate are automatically maintained and regulated according to on-line monitored values and variation trends of water vapor content and hot spot temperature of reduction tail gas. With the method, controlling over catalyst reduction furnace automatic reduction can be realized; an entire reduction process can be monitored; an entire catalyst reduction time can be reduced; and a hydrogen usage amount can be reduced. Therefore, the processing period and the processing cost of the catalyst are greatly reduced.
Description
Technical field
The present invention relates to a kind of catalyst reduction method, more particularly, relate to a kind of method for the catalyst fast restore.
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 catalyst majority that uses in petrochemical production process belongs to solid catalyst, is comprised of carrier, auxiliary agent and active component three parts, and wherein the precursor of active component mostly is metallic salt.Most catalyst activity components only have for metallic atom loads on carrier and just can have catalytic activity in commercial Application, therefore carry out pyrolytic and become oxidation state with regard to must loading on carrier slaine, then reduce the catalyst finished product that just can obtain having active sites.In catalyst, the reduction effect of metal oxide is determining the quality of catalyst catalytic performance.Thereby the catalyst reduction passivating process is the step of an outbalance in industrial catalyst finished product production process.
At present, mostly the reduction process factory of catalyst is to adopt temperature-programmed technique to carry out under certain hydrogen flowing quantity, if can be divided into manual adjustments and automatically regulate according to temperature regulation mechanism.Manual adjustments is that the temperature and time of the prior predetermined section of basis carries out manually temperature programming piecemeal, can take to reduce amounts of hydrogen and regulate the temperature rise cooling if occur temperature runaway in reduction process; Automatically adjusting is that heating schedule is set on instrument, and the centre can not change, and only has by reducing amounts of hydrogen and lowers the temperature if occur temperature runaway in reduction process.Although above-mentioned dual mode all has advantage, drawback is that the recovery time of catalyst is long, hydrogen gas consumption is large etc., thereby will cause long and high in cost of production of catalyst process-cycle.
Summary of the invention
The problem of, hydrogen gas consumption long for the ubiquitous catalyst reduction time in present industrial production, the inventor is on the basis of existing operation, water vapor concentration in on-line analysis reduction furnace tail gas utilizes the reduction control program of control system to analyze hydrogen flowing quantity and the heating rate parameter that data are adjusted reduction furnace.Result of the test is found, use the autocontrol method of fast restore of the present invention, can be original 70%～85% with the catalyst reduction time shorten, hydrogen gas consumption is original 65%～80%, not only shortened the recovery time of catalyst, improve the annual production of reduction furnace, and reduced the reduction cost of catalyst.
Concrete technical scheme is as follows:
The method of catalyst rapid reducing of the present invention, in the catalyst reduction process, water vapor concentration in on-line analysis reduction furnace tail gas, as a result in the control system of enter catalyst reduction apparatus, control system is adjusted the hydrogen flowing quantity of reduction furnace or/and reduction temperature according to the on-line analysis result with on-line analysis.
Preferably, with the mist reducing catalyst of nitrogen and hydrogen, the volume space velocity of nitrogen is 1～1000h
-1, keeping the reduction parameter constant after at least 10 minutes, if water vapor concentration 〉=0.05% in reduction furnace tail gas is set as hydrogen flowing quantity 60%～80% of initial setting flow; If in reduction furnace tail gas, water vapor concentration is less than 0.05%, at first hydrogen flowing quantity is adjusted to the initial setting flow of control system, if in reduction furnace tail gas, water vapor concentration is still less than 0.05%, then the reduction temperature that raises; When reduction temperature reaches catalyst during high reduction temperature, keep the reduction parameter constant, until water vapor concentration is less than 0.01%, reduction process finishes to lower the temperature.
Preferably, analyze the water vapor concentration in reduction furnace tail gas No. one time every 2～10min.
Preferably, the initial setting hydrogen flowing quantity in the volume hourly space velocity, is 3.0～1000.0h
-1
Preferably, the heating rate of rising reduction temperature is 5～20 ℃, and more preferably, heating rate is 10～15 ℃.
Preferably, the highest reduction temperature must not be higher than 440 ℃, more preferably must not be higher than 420 ℃.
In the present invention, if do not particularly point out, described concentration all refers to volume percent content, and described flow all refers to mass flow.
The online fast restore process of catalyst is altogether in three steps: the reducing program starting stage; The reduction furnace heating reduction stage; Reduction furnace reduction termination phase.The execution sequence of fast restore control method is as follows:
1, the reducing program starting stage
After the startup of reduction control program, at first give the built-in variables such as initial hydrogen throughput and initial heating rate, and automatically identify the analysis result signal of reduction tail gas online analytical instrument.
Confirm that all execute-in-places all are finished, on-the-spot on-line analysis device data access is normal, and has been ready to enter automatic control reduction phase, as not confirmed program be in wait state, until all confirm, clicked to begin to enter by operating personnel and reduce the automatic control stage.
2, the reduction furnace heating reduction stage
After entering the reduction automatic control program, the reduction control program obtains the data such as water vapor concentration and hot(test)-spot temperature in the reduction tail gas of field assay instrument on-line analysis by the reduction control system, and foundation reduction tails assay data judge whether to need to adjust the control variables of reduction furnace, realize the automatic control of each parameter of reduction process, until whole reduction process finishes.At least after making water vapor concentration and hot(test)-spot temperature satisfy condition after each parameter of adjustment reduction, can again adjust each parameter.
3, reduction furnace reduction termination phase
When the reduction control program monitors catalyst during high reduction temperature, the cooling of program automatic alarm reduction apparatus enters the catalyst structure stage.Manually stop reducing control program by operating personnel.
The method of catalyst rapid reducing 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, has advantages of save time and save hydrogen, makes the active component particle of catalyst grow up not obvious because the recovery time is short.
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, and scope of the present invention proposes in claims one by one.
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, nitrogen flow is 125m
3/ h, the initial hydrogen throughput is 375m
3/ h, the concrete steps of traditional method of reducing and the inventive method see Table 1.Catalyst through reduction is 0.5h at 152 ℃, acetone volume space velocity
-1, acetone: hydrogen: the mol ratio of ammonia is 1: 3: 3, and catalyst amount is on the isopropylamine evaluating apparatus of 50ml and estimates, and evaluation result sees Table 2.
Adopt the concrete operation of method of the present invention as follows: setting reduction furnace initial heating speed is 10 ℃/h, and nitrogen flow is 125m
3/ h, the initial hydrogen throughput is 375m
3/ h opens the reduction control program and heats up, and carries out water vapor concentration in on-line analysis reduction tail gas every 10min, and when furnace temperature rose to 160 ℃, beginning to detect vapour content was 0.015%; When being warming up to 200 ℃, vapour content being detected is 0.06%, and it is 0 that the control program that reduces this moment is regulated heating rate, and hydrogen flowing quantity is 260m
3/ h after keeping temperature 1h, analyzes the discovery water vapor concentration and is down to 0.03%, and hydrogen flowing quantity is adjusted to 375m
3/ h analyze to find water vapor concentration still less than 0.05%, with the heating rate rising reduction temperature of 10 ℃/h, when temperature rises to 230 ℃, it is 0.06% that on-line analysis detects vapour content, and it is 0 that the reduction control program is regulated heating rate, and hydrogen flowing quantity is 260m
3/ h learns that through detecting after 2h water vapor concentration is down to 0.025%, and hydrogen flowing quantity is adjusted to 375m
3/ h analyze to find water vapor concentration still less than 0.05%, with the heating rate rising reduction temperature of 10 ℃/h; After temperature rose to 350 ℃, in tail gas, water vapor concentration had reached 0.05%, and this moment, reducing program just regulated 0 with heating rate, and hydrogen flowing quantity is adjusted to 260m
3/ h detects tail gas again after 2h, find that water vapor concentration will be 0.03%, and hydrogen flowing quantity is adjusted to 375m
3/ h analyzes and finds that water vapor concentration is still less than 0.05%; For this reason with the heating rate rising reduction temperature of 10 ℃/h, temperature is reduced tail gas inspection results in the time of 400 ℃ be that water vapor concentration is 0.03%, until continue to heat up 420 ℃, keeps having can't detect water vapour in tail gas after 1h, the reduction control program stops, and the whole reduction of catalyst is completed.
The table 1 catalyst reduction step table of comparisons
The contrast of table 2 evaluating catalyst result
Can be found out by data in table 1, method of the present invention total recovery time used is 72% of the tradition recovery time, and the hydrogen consumption total amount is 71% 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 original method.Therefore, autocontrol method of the present invention has also reduced the reduction cost of catalyst guaranteeing not only to have shortened the recovery time of catalyst on the basis that catalyst fully reduces.
Claims (7)
1. the method for a catalyst rapid reducing, it is characterized in that, in the catalyst reduction process, water vapor concentration in on-line analysis reduction furnace tail gas, as a result in the control system of enter catalyst reduction apparatus, control system is adjusted the hydrogen flowing quantity of reduction furnace or/and reduction temperature according to the on-line analysis result with on-line analysis; Keeping the reduction parameter constant after at least 10 minutes, if water vapor concentration 〉=0.05% in reduction furnace tail gas; Hydrogen flowing quantity is reduced 20%～40%; If in reduction furnace tail gas, water vapor concentration is less than 0.05%, at first hydrogen flowing quantity is adjusted to the initial setting flow of control system, if in reduction furnace tail gas, water vapor concentration is still less than 0.05%, then with the heating rate rising reduction temperature of 20～30 ℃/h; When reduction temperature reaches catalyst during high reduction temperature, keep the reduction parameter constant, until water vapor concentration is less than 0.01%, reduction process finishes to lower the temperature.
2. the method for claim 1, is characterized in that, analyzes the water vapor concentration in reduction furnace tail gas No. one time every 2～10min.
3. the method for claim 1, is characterized in that, the initial setting hydrogen flowing quantity in the volume hourly space velocity, is 3.0～5.0h
-1
4. the method for claim 1, is characterized in that, initial heating rate is 5～20 ℃.
5. the method for claim 1, is characterized in that, initial heating rate is 10～15 ℃.
6. the method for claim 1, is characterized in that, the highest reduction temperature must not be higher than 440 ℃.
7. the method for claim 1, is characterized in that, the highest reduction temperature must not be higher than 420 ℃.
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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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2010
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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 (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),1-8. |
| 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 * |
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