CN102863331A - Terephthalic acid hydrofining catalyst activity status judgment method - Google Patents
Terephthalic acid hydrofining catalyst activity status judgment method Download PDFInfo
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Abstract
The invention relates to a terephthalic acid hydrofining catalyst activity status judgment method. The activity status the catalyst is judged according to the mass ratio of p-methylbenzoic acid to p-hydroxymethylbenzoic acid: when the mass ratio of p-methylbenzoic acid to p-hydroxymethylbenzoic acid is greater than 3, the catalyst is in the activity earlier stage; when the mass ratio of p-methylbenzoic acid to p-hydroxymethylbenzoic acid is 2-3, the catalyst is in the activity stable stage; when the mass ratio of p-methylbenzoic acid to p-hydroxymethylbenzoic acid is 1.6-2, the catalyst is in the activity later stage; and when the mass ratio of p-methylbenzoic acid to p-hydroxymethylbenzoic acid is smaller than 1.6, the catalyst is in an inactive stage, and the catalyst needs to be treated. The technological conditions for reaction are regulated according to the activity status of the catalyst, so that the catalyst activity can be kept in the stable stage for a long time, and the usage time of the catalyst can be prolonged.
Description
Technical field
The present invention relates to the active situation determination methods of a kind of terephthalic acid Hydrobon catalyst, belong to chemical field, especially terephthalic acid hydrogenation catalyst field.
Background technology
Terephthalic acid (hereinafter to be referred as TA) Hydrobon catalyst is in use active constantly to descend, and its major cause is inactivation in use.TA Hydrobon catalyst inactivation can be divided into permanent deactivation and temporary transient inactivation.Management by adding powerful catalyst, strictly control the operational condition such as temperature, pressure of reactor and take full advantage of old catalyzer and can control the catalyzer permanent deactivation with type of feed of improving catalyzer etc.The temporary transient inactivation of catalyzer is mainly descended by catalyst specific surface, blockage of the micro orifice, the factors such as metal deposition cause, can process by the method for washing and alkali cleaning, catalyst activity is restored, the situation of temporary transient inactivation can repeatedly appear in catalyzer in life cycle, need to judge the active situation of catalyzer, present industrial judgement catalyst deactivation main method is the content of analyzing in poly terephthalic acid (hereinafter to be referred as the PTA) product carboxyl benzaldehyde (hereinafter to be referred as 4-CBA), when the content of 4-CBA in the product during near 25ppm, think that catalyst activity is reduced to unacceptable degree, need to process catalyzer.And in actual production, because it is not obvious that reactor exit 4-CBA changes, 4-CBA content can not produce sudden change because catalyst activity changes in the product, and the activity of judging accordingly catalyzer has hysteresis quality to a certain degree, thereby affects the catalyst treatment grasp on opportunity.Therefore need to seek a kind of method of judging that in time, accurately catalyst activity changes.
Summary of the invention
The invention provides the active situation determination methods of a kind of terephthalic acid Hydrobon catalyst, can judge in time, exactly TA Hydrobon catalyst activity change, so that TA hydrofining cell process carries out the treatment time that corresponding process optimization and TA hydrogenation catalyst obtain suiting, thereby prolong TA Hydrobon catalyst duration of service.
The active situation determination methods of described terephthalic acid Hydrobon catalyst is, analyze the composition of terephthalic acid hydrofining reaction product, with p-methylbenzoic acid wherein and mass ratio to hydroxymethyl-benzoic acid, judge the active situation of catalyzer, when p-methylbenzoic acid with to the hydroxymethyl-benzoic acid mass ratio greater than 3 the time, catalyzer is in active early stage; When p-methylbenzoic acid and to the hydroxymethyl-benzoic acid mass ratio between 2 and 3 the time, catalyzer is in active stabilization period; When p-methylbenzoic acid and to the hydroxymethyl-benzoic acid mass ratio between 1.6 and 2 the time, catalyzer is in the active later stage; When p-methylbenzoic acid with to the hydroxymethyl-benzoic acid mass ratio less than 1.6 the time, catalyzer is in the inactivation phase, needs process catalyzer.
Above-mentioned catalyzer is in different activities during the stage, adopts the processing condition of different TA hydrofining reactions.At catalyst activity in earlier stage, because catalyst activity is higher, need to reduce hydrogen flowing quantity, with the generation that control catalyzer excessive hydrogenation is reacted, therefore adopt normal temperature of reaction and lower hydrogen flowing quantity, hydrogen flowing quantity is 80%～90% of normal running; In catalyst activity stationary phase, because catalyst activity is stable, hydrogenation process is more stable, therefore adopt normal temperature of reaction and normal hydrogen flowing quantity; In the catalyst activity later stage, because catalyst activity is lower, therefore need the method by process strengthening, improve catalyst activity, therefore adopt higher temperature of reaction and higher hydrogen flowing quantity, temperature of reaction improves 1～2 ℃ on the basis of normal running temperature, and hydrogen flowing quantity improves 10%～20% on the basis of normal running.Described normal temperature of reaction is defined as 282 ℃ according to the AMOCO hydrogenation technique, and described normal hydrogen flowing quantity is according to the device capbility situation, and 300,000 ton/years of device hydrogen flowing quantities are 12kg/h.Behind the catalyst activity adjusting process, the reaction product composition can change, and is mainly manifested in 4-CBA content in the PTA product, the PT acid content diminishes, the PTA better quality.
Above-mentioned p-methylbenzoic acid be to the mass ratio of hydroxymethyl-benzoic acid after the sampling of PTA device, through liquid-phase chromatographic analysis obtain respectively p-methylbenzoic acid with to hydroxymethyl-benzoic acid in solid phase mass concentration and the mass concentration in the liquid phase, then the liquid-solid ratio by when sampling convert obtain after the PTA hydrogenation reaction p-methylbenzoic acid in the product with to the hydroxymethyl-benzoic acid mass concentration.The conditions such as the concentration by adjusting liquid chromatogram mobile phase, pH value, flow velocity can and be separated the hydroxymethyl-benzoic acid peak fully with the p-methylbenzoic acid peak under suitable absorbing wavelength.Concrete analysis condition is as follows: chromatographic column: Zorbax SAX 4.6mm * 250mm stainless steel, moving phase: 0.25mol NH
4H
2PO
4, 10% acetonitrile, flow velocity 1.0mL/mol, column temperature: 25 ℃.
Described p-methylbenzoic acid be to obtain when under normal operating condition, carrying out hydrofining reaction to the mass ratio of hydroxymethyl-benzoic acid, obtain when carrying out hydrofining reaction under the trained operational condition of the active situation of catalyzer before also can being.Describedly carrying out operational condition before the reaction process condition adjustment according to the catalyst activity situation, both can be normal operating condition, also can be before the operational condition trained according to the situation of catalyzer.For example, if adopt normal operational condition before the TA hydrofining unit, then can directly under normal operating condition, obtain p-methylbenzoic acid with to the mass ratio of hydroxymethyl-benzoic acid, and judge TA Hydrobon catalyst activity situation according to the present invention; If adopted the present invention to judge the active situation of TA Hydrobon catalyst before the TA hydrofining unit, and adjusted accordingly the processing condition of hydrofining reaction, so under the operational condition after this adjusts the monitoring p-methylbenzoic acid with to the hydroxymethyl-benzoic acid mass ratio, when this mass ratio shows that variation has occured the active situation of catalyzer, then adjust accordingly the processing condition of hydrofining reaction.
The present invention according to each component concentration in the hydrogenation products the catalyst activity situation is judged, and proposes corresponding art treatment by TA hydrofining reaction product composition is analyzed.Adopt method of the present invention, can in time, effectively judge TA Hydrobon catalyst active condition, according to catalyzer active condition of living in, adopt the processing condition of corresponding TA hydrofining reaction, TA Hydrobon catalyst performance is brought into play preferably, but the long term keeps catalyst activity to be in stationary phase, and 4-CBA content, PT acid content keep stable in the product, and catalyzer is prolonged duration of service.
Embodiment
The following examples will be described further method provided by the invention, but the present invention is not limited to embodiment.
Embodiment 1
Certain TA of PTA factory hydrofining reaction process is followed the tracks of, and the composition of analytical reaction product to the judgement of catalyst activity situation, and adopts the processing condition of corresponding TA hydrofining reaction.This batch of catalyzer is before using processing condition of the present invention, and catalyzer average duration of service is 18 months, the processing condition that adopt the present invention to propose, and catalyzer reaches 21.5 months duration of service, has improved 19.4% average duration of service than this catalyzer.
Catalyst activity early stage, p-methylbenzoic acid is with as shown in table 1 to hydroxymethyl-benzoic acid representative value and processing condition.
Table 1 catalyst activity representative value in early stage and processing condition
Catalyst activity mid-term, p-methylbenzoic acid is with as shown in table 2 to hydroxymethyl-benzoic acid representative value and processing condition.
Table 2 catalyst activity representative value in mid-term and processing condition
In the catalyst activity later stage, p-methylbenzoic acid is with as shown in table 3 to hydroxymethyl-benzoic acid representative value and processing condition.
Table 3 catalyst activity later stage representative value and processing condition
The catalyst deactivation phase, p-methylbenzoic acid is with as shown in table 4 to the hydroxymethyl-benzoic acid representative value.
Table 4 catalyst deactivation phase representative value
Claims (3)
1. the active situation determination methods of a terephthalic acid Hydrobon catalyst, it is characterized in that, analyze the composition of terephthalic acid hydrofining reaction product, with p-methylbenzoic acid wherein and mass ratio to hydroxymethyl-benzoic acid, judge the active situation of catalyzer, when p-methylbenzoic acid with to the hydroxymethyl-benzoic acid mass ratio greater than 3 the time, catalyzer is in active early stage; When p-methylbenzoic acid and to the hydroxymethyl-benzoic acid mass ratio between 2 and 3 the time, catalyzer is in active stabilization period; When p-methylbenzoic acid and to the hydroxymethyl-benzoic acid mass ratio between 1.6 and 2 the time, catalyzer is in the active later stage; When p-methylbenzoic acid with to the hydroxymethyl-benzoic acid mass ratio less than 1.6 the time, catalyzer is in the inactivation phase, needs process catalyzer.
2. described determination methods gained catalyst activity situation is carried out the hydrorefined method of terephthalic acid according to claim 1, it is characterized in that, when catalyzer is in active early stage, normal temperature of reaction is adopted in terephthalic acid hydrofining, and hydrogen flowing quantity is 80%～90% of normal hydrogen airshed; When catalyzer was in active stabilization period, terephthalic acid hydrofining was with normal temperature of reaction and normal hydrogen flowing quantity; When catalyzer was in the active later stage, terephthalic acid hydrofining reaction temperature improved 1～2 ℃ on the basis of well-defined reaction temp, and hydrogen flowing quantity is 110%～120% of normal hydrogen airshed.
3. the hydrorefined method of terephthalic acid as claimed in claim 2 is characterized in that, when catalyzer was in active stabilization period, terephthalic acid hydrofining was with normal temperature of reaction and normal hydrogen flowing quantity; Described normal temperature of reaction is defined as 282 ℃ according to the AMOCO hydrogenation technique, and described normal hydrogen flowing quantity is according to the device capbility situation, and 300,000 ton/years of device hydrogen flowing quantities are 12kg/h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4892972A (en) * | 1985-10-07 | 1990-01-09 | Amoco Corporation | Purification of crude terephthalic acid |
| US5387726A (en) * | 1993-01-08 | 1995-02-07 | Degussa Aktiengesellschaft | Selective catalytic hydrogenation of aromatic aldehydes |
| US6706658B2 (en) * | 2001-12-21 | 2004-03-16 | Engelhard Corporation | Catalyst for purification of aromatic acids |
| CN102247839A (en) * | 2010-05-17 | 2011-11-23 | 中国石油化工股份有限公司 | Smooth transition method for initial activity of palladium-carbon catalyst |
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2012
- 2012-09-18 CN CN201210346549.7A patent/CN102863331B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4892972A (en) * | 1985-10-07 | 1990-01-09 | Amoco Corporation | Purification of crude terephthalic acid |
| US5387726A (en) * | 1993-01-08 | 1995-02-07 | Degussa Aktiengesellschaft | Selective catalytic hydrogenation of aromatic aldehydes |
| US6706658B2 (en) * | 2001-12-21 | 2004-03-16 | Engelhard Corporation | Catalyst for purification of aromatic acids |
| CN102247839A (en) * | 2010-05-17 | 2011-11-23 | 中国石油化工股份有限公司 | Smooth transition method for initial activity of palladium-carbon catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 周静红等: "对苯二甲酸的加氢精制过程"", 《华东理工大学学报（自然科学版）》 * |
| 王昱等: "延长Pd/ C 催化剂使用寿命", 《聚酯工业》 * |
| 章颖等: "延长Pd/C 催化剂使用寿命的探讨", 《聚酯工业》 * |
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