CN102863331B - 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 decline, and its major cause is inactivation in use.TA Hydrobon catalyst inactivation can be divided into permanent deactivation and temporary transient inactivation.By adding the management of powerful catalyst, strictly control the operational condition such as temperature, pressure of reactor and make full use of old catalyzer and can control catalyzer permanent deactivation with type of feed of improving catalyzer etc.The temporary transient inactivation of catalyzer is mainly declined 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, in life cycle, can repeatedly there is the situation of temporary transient inactivation in catalyzer, need to judge the active situation of catalyzer, current industrial judgement catalyst deactivation main method is to analyze the content to carboxyl benzaldehyde (hereinafter to be referred as 4-CBA) in poly terephthalic acid (hereinafter to be referred as PTA) product, in the time that the content of 4-CBA in product approaches 25ppm, think that catalyst activity is reduced to unacceptable degree, need to process catalyzer.And in actual production, because reactor exit 4-CBA changes not obvious, in product, 4-CBA content can not produce sudden change because catalyst activity changes, and judge that accordingly the activity of catalyzer has hysteresis quality to a certain degree, thereby impact is to the catalyst treatment grasp on opportunity.Therefore need to find a kind of method that judges 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 corresponding process optimization and TA hydrogenation catalyst obtains the suitable treatment time, thereby extend 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 is when being greater than 3 to hydroxymethyl-benzoic acid mass ratio, catalyzer is in activity early stage; When p-methylbenzoic acid and to hydroxymethyl-benzoic acid mass ratio between 2 and 3 time, catalyzer is in active stabilization period; When p-methylbenzoic acid and to hydroxymethyl-benzoic acid mass ratio between 1.6 and 2 time, catalyzer is in the active later stage; When p-methylbenzoic acid is when being less than 1.6 to hydroxymethyl-benzoic acid mass ratio, catalyzer, in the inactivation phase, need be processed catalyzer.
Above-mentioned catalyzer, in the time of the different activities stage, adopts the processing condition of different TA hydrofining reactions.In catalyst activity early stage, because catalyst activity is higher, need to reduce hydrogen flowing quantity, to control the generation of catalyzer excessive hydrogenation reaction, therefore adopt normal temperature of reaction and lower hydrogen flowing quantity, hydrogen flowing quantity is normal running 80%～90%; 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 DEG C 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 DEG C according to AMOCO hydrogenation technique, and described normal hydrogen flowing quantity is according to device capbility situation, and 300,000 tons/year of device hydrogen flowing quantities are 12kg/h.According to after catalyst activity adjusting process, reaction product composition can change, and is mainly manifested in 4-CBA content in PTA product, PT acid content diminishes, PTA better quality.
Above-mentioned p-methylbenzoic acid be to the mass ratio of hydroxymethyl-benzoic acid from PTA device sampling, obtain respectively p-methylbenzoic acid and the mass concentration in mass concentration and the liquid phase in solid phase to hydroxymethyl-benzoic acid through liquid-phase chromatographic analysis, then by the liquid-solid ratio in when sampling convert obtain after PTA hydrogenation reaction the p-methylbenzoic acid in product with to hydroxymethyl-benzoic acid mass concentration.By adjusting the condition such as concentration, pH value, flow velocity of liquid chromatogram mobile phase, under suitable absorbing wavelength, can and separate completely hydroxymethyl-benzoic acid peak p-methylbenzoic acid peak.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 DEG C.
Described p-methylbenzoic acid be to obtain carry out hydrofining reaction under normal operating condition time 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 can being also.Describedly carrying out the operational condition before reaction process condition adjustment according to catalyst activity situation, can be both normal operating condition, can be also before the operational condition trained according to the situation of catalyzer.For example, if adopt normal operational condition before TA hydrofining unit, can directly under normal operating condition, obtain p-methylbenzoic acid and the mass ratio to hydroxymethyl-benzoic acid, and judge the active situation of TA Hydrobon catalyst according to the present invention; If adopted the present invention to judge the active situation of TA Hydrobon catalyst before TA hydrofining unit, and adjusted accordingly the processing condition of hydrofining reaction, so this adjust after operational condition under monitor p-methylbenzoic acid with to hydroxymethyl-benzoic acid mass ratio, in the time that this mass ratio shows that variation has occurred the active situation of catalyzer, adjust accordingly the processing condition of hydrofining reaction.
The present invention, by TA hydrofining reaction product composition is analyzed, according to each component concentration in hydrogenation products catalyst activity situation is judged, and proposes corresponding art treatment.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, can make TA Hydrobon catalyst performance be brought into play preferably, can keep catalyst activity in stationary phase the long term, in product, 4-CBA content, PT acid content keep stable, and catalyzer is extended 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 using before 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.
In earlier stage, p-methylbenzoic acid is with as shown in table 1 to hydroxymethyl-benzoic acid representative value and processing condition for catalyst activity.
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 hydroxymethyl-benzoic acid representative value.
Table 4 catalyst deactivation phase representative value
Claims (3)
1. the active situation determination methods of 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 is when being greater than 3 to hydroxymethyl-benzoic acid mass ratio, catalyzer is in activity early stage; When p-methylbenzoic acid and to hydroxymethyl-benzoic acid mass ratio between 2 and 3 time, catalyzer is in active stabilization period; When p-methylbenzoic acid and to hydroxymethyl-benzoic acid mass ratio between 1.6 and 2 time, catalyzer is in the active later stage; When p-methylbenzoic acid is when being less than 1.6 to hydroxymethyl-benzoic acid mass ratio, catalyzer, in the inactivation phase, need be processed catalyzer.
2. determination methods gained catalyst activity situation is carried out the hydrorefined method of terephthalic acid according to claim 1, it is characterized in that:
Compare catalyzer in the time of active stabilization period, the hydrorefined temperature of reaction of terephthalic acid and hydrogen flowing quantity;
Catalyzer is in activity when early stage, and the temperature of reaction that terephthalic acid hydrofining adopts and hydrogen flowing quantity are 80%～90% of the temperature of reaction of catalyzer in the time of active stabilization period and hydrogen flowing quantities;
Catalyzer is in the time of the active later stage, and the temperature of reaction of the hydrorefined temperature of reaction of terephthalic acid during than catalyst activity stationary phase improves 1～2 DEG C, 110%～120% of hydrogen flowing quantity when hydrogen flowing quantity is catalyst activity stationary phase.
3. the hydrorefined method of terephthalic acid as claimed in claim 2, is characterized in that, catalyzer in the time of active stabilization period, normal temperature of reaction and normal hydrogen flowing quantity for terephthalic acid hydrofining; Described normal temperature of reaction is defined as 282 DEG C according to AMOCO hydrogenation technique, and described normal hydrogen flowing quantity is according to device capbility situation, and 300,000 tons/year of device hydrogen flowing quantities are 12kg/h.
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Citations (4)
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|---|---|---|---|---|
| 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
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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 (6)
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| 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）》.2006,第32卷(第4期),第374-380页. |
| 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)》.2006,第32卷(第4期),第374-380页. * |
| 延长Pd/ C 催化剂使用寿命;王昱等;《聚酯工业》;20010630;第14卷(第3期);第15-17页 * |
| 延长Pd/C 催化剂使用寿命的探讨;章颖等;《聚酯工业》;20000331;第13卷(第1期);第41-43页 * |
| 王昱等.延长Pd/ C 催化剂使用寿命.《聚酯工业》.2001,第14卷(第3期),第15-17页. |
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