CN101724100B - Catalyst pretreatment method - Google Patents
Catalyst pretreatment method Download PDFInfo
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- CN101724100B CN101724100B CN2008102248646A CN200810224864A CN101724100B CN 101724100 B CN101724100 B CN 101724100B CN 2008102248646 A CN2008102248646 A CN 2008102248646A CN 200810224864 A CN200810224864 A CN 200810224864A CN 101724100 B CN101724100 B CN 101724100B
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Abstract
The invention provides a catalyst pretreatment method for preparing paste catalyst, is particularly applicable to an olefin polymerization catalyst. The method comprises the following steps: connecting a catalyst preparing tank, a preparation circulating pump and a filter in series through material circulating pipelines to form a circulating loop; leading the catalyst preparations out from the bottom of the preparing tank after the preparation process is completed, filtering large grain size solid impurities in the preparations by the filter after the preparations are pressurized by the circulating pump, sending the preparations back to the preparing tank from the upper part of the preparing tank through the circulating loop; and conveying the catalyst from the filter to a catalyst feed pump according to the requirement when the catalyst is needed by a polymerization device downstream. The method ensures that the catalyst preparations are even, the impurities in the preparations can be removed, and a pressure head is provided to send the catalyst preparations to the catalyst feed pump so as to solve the problem in aspect of equipment caused by overhigh raising pressure of the preparing tank. The catalyst pretreatment method ensures that the outlet pressure of the catalyst feed pump is remarkably lower, and catalyst feed is stable without blocking.
Description
Technical field
The present invention relates to a kind of catalyst pretreatment method that is used to be mixed with paste.Further relate to a kind of pretreatment process that is used to be mixed with the olefin polymerization catalysis of paste.
Technical background
Usually use efficiently catalyzer in the polyolefin industry to realize polyreaction.Along with development of technology, activity of such catalysts is unusual height usually, thereby in use need carry out the dilution of catalyzer, causes that polymer lumps, polyreaction temperature runaway etc. are unusual otherwise a large amount of catalyzer adds affiliation, influences the operation of device.Polyolefin catalyst is generally solid, and the method for dilution has multiple.Can use inert organic solvents, catalyst preparation become certain density slurries, catalyzer is sent to follow-up reactor drum with metered charge facilities such as volume pumps such as white oil, hexane etc.Also can catalyst preparation be become certain density paste with hydrocarbon ils, hydrocarbon fat etc., with there being certain volumetrical syringe pump that it is delivered to follow-up reactor drum, the volume of pump can be kept several hours catalyst charge amount usually again.Two kinds of methods comparatively speaking, the former because of catalyzer easily in preparation, some link or the position sedimentation of carrying, the precision of influence metering and the stability of conveying are a kind of relative backward technologies.The latter can avoid above-mentioned unfavorable factor comparatively speaking, accurate measurement, and fill process is steady, thereby use is more.Such as on Vestolen PP 7052 endless tube process unit, the charging of catalyzer is adopted exactly should technology.
The preparation of existing catalyzer paste is in the equipment that a vertical awl tail band ribbon stirs, to carry out.Earlier hydrocarbon ils, hydrocarbon fat are risen to certain temperature, after the method dehydration that vacuumizes with heating, the deoxidation treatment, add catalyzer, reduce to the low temperature below 10 ℃ again, make enough big of the viscosity of system, to avoid the layering of catalyzer and hydrocarbon ils, hydrocarbon fat.This process is because consideration later stage system viscosity is very big, thereby stirring can only be designed to slow-revving ribbon.And this ribbon is very poor for the mixing effect of awl bottom branch.On the other hand, when adding catalyzer, because the proportion of catalyzer is bigger, mixing effect is poor, and system viscosity is little, and catalyzer very easily is deposited on the awl bottom of preparing tank and divides.High and some the impurity depositions of this catalyst concn that has just caused preparing tank awl bottom to divide.Such catalyzer at first because viscosity is big, can cause line of pipes pressure superelevation in use; Moreover, block impurity is arranged because concentration is high, and be prone to the blocking catalyst feeding line, influence the steady running of follow-up polymeric kettle, the danger of the process of block clearing is also very big.When concrete industrial application, the someone adopts the mode of " batch turning " to reduce its influence.So-called " batch turning " process is, the catalyst charge pump has two, and the A pump is filled the catalyst preparation thing for preparing earlier; The B pump also is filled catalyzer subsequently; Then the catalyst preparation thing in the A pump is sent back in the preparing tank, the catalyzer of B pump is also all sent back to again, original like this catalyst preparation thing that is deposited on the overrich of preparing tank bottom will be pulled to position last in the jar; Under stirring action, can mix with the formulation at other position.But this process need stops catalyst charge and carries out the batch turning operation, influences the steady running of device.Impurity in the formulation can not be removed in addition, thereby this method has tangible deficiency.
The present invention will provide a kind of catalyst preparation thing pretreated method; Can make the catalyst preparation thing evenly, can also remove impurity wherein simultaneously; Can also provide the catalyst preparation thing is delivered to the catalyst charge thrust of pump, thereby avoid the boost problem of the too high equipment aspect of bringing of preparing tank.
Summary of the invention
A kind of catalyst pretreatment method that is used for catalyst preparation is become paste, this catalyst pretreatment method comprise catalyst preparation jar (1), formulation recycle pump (2), strainer (3); With the material circulation line above-mentioned three devices in series are got up, form circulation loop, described catalyst preparation jar is the container that has the preparation catalyzer of stirring; The inlet that the top of preparing tank has catalyzer and makes up oil; After process for preparation is accomplished, the catalyst preparation thing is drawn from preparing pot bottom, after the recycle pump supercharging; Leach big particle diameter solid impurity wherein with strainer; The catalyst preparation thing sends back to preparing tank through circulation loop from the top of preparing tank, gets together for fun instantly when closing the equipment claimed catalyzer, and the catalyzer that comes out from strainer (3) is delivered to the catalyst charge pump on demand.
As shown in Figure 1, outside the catalyst preparation jar, increase a catalyst preparation thing recycle pump, pump outlet is provided with a strainer.Accomplish the preparation of catalyzer paste by common compound method; After process for preparation is accomplished, the catalyst preparation thing is drawn from preparing pot bottom, after the recycle pump supercharging; Leach big particle diameter solid impurity wherein with strainer, formulation sends back to preparing tank from the top of preparing tank.This process keeps the whisking appliance of preparing tank to run well, and (is generally and doubles its residence time in preparing tank) behind the catalyst preparation thing circulation certain hour, stops the circulation of catalyst preparation thing.After reaching, add the catalyst preparation thing to follow-up catalyst charge pump if desired around here, can the valve open of circulating-pump outlet end strainer back be discharged a certain amount of formulation to catalyst charge pump.
Catalyst preparation thing of the present invention is meant that this catalyzer is the solid olefin polymerization catalysis, but is not limited to olefin polymerization catalysis with the catalyzer paste after hydrocarbon ils and/or the dilution of hydrocarbon fat.Hydrocarbon ils, the hydrocarbon fat that is used for catalyst preparation can be that aliphatic compound, its mixture of arene compounds and other can be used for the material of catalyst preparation, and its foreign matter content is not higher than the amount that makes catalyzer lose katalysis.
Described catalyst recirculation pump can be that spiral pump, peristaltic pump, steam piano, toothed gear pump, surge pump, syringe pump and other can be used for the equipment that the catalyst preparation thing is carried.
Strainer on the said catalyst recycle line can be that deep bed filter, y-type filter, T type filter and other are used for the strainer of different-grain diameter separating substances.The filtering material of strainer can be but be not limited only to wire cloth, sintered metal sheet, fiber twister etc.
Description of drawings
Fig. 1 catalyst preconditioning process synoptic diagram.
The explanation of concrete accompanying drawing sees also summary of the invention
Comparative Examples and embodiment
Comparative Examples:
Said Comparative Examples is carried out on a cover 25kg/hr Vestolen PP 7052 endless tube pilot plant.
The catalyzer that the method for describing among the catalyzer employing Chinese patent CN93102795.0 obtains, its Ti content is 2.4Wt%, and Mg content is 18.0Wt%, and n-butyl phthalate content is 13Wt%.Adopt methylcyclohexyl dimethoxy silane (CH
3C
6H
11-Si-(OCH
3)
2, be external electron donor CHMMS), with hydrogen molecular weight regulator.
Adopt annular-pipe reactor liquid phase body propylene continuous polymerization technique to prepare Vestolen PP 7052.The hydrocarbon ils of 2kg, hydrocarbon fat (mixing by weight 2:1) are joined in the catalyst preparation jar, be heated to 70 ℃, be evacuated to that < 0.07MPaG kept 2 hours.Add the 120g catalyzer, blast nitrogen from following bottom valve, nitrogen amount is 0.5Nm
3/ hr kept 1 hour.Be cooled to 20 ℃, vacuumize (0.07MPaG) 0.5 hour, continue to be cooled to below 10 ℃ and maintenance.So far, accomplish catalyst preparation, can normally use.Catalyst preparation jar band ribbon stirs, 30 rev/mins of rotating speeds.
The catalyst preparation thing joins in the preparatory contact jar after the metering of catalyst charge pump, contacts in advance with triethyl aluminum, CHMMS, and the condition of contact is 10 ℃ in advance, 20min; Catalyzer after the contact is brought prepolymerization reactor into 10 ℃ cold propylene, 15 ℃ of prepolymerization temperature, 6 minutes prepolymerization time in advance; Catalyzer after the pre-polymerization gets into first annular-pipe reactor and second annular-pipe reactor successively, 70 ℃ of endless tube polymeric reaction temperatures, reaction pressure 4.1MPaG.The residence time in two annular-pipe reactors is respectively 65min and 50min; The material flash separation of coming out from annular-pipe reactor, take off and live, after the drying treatment, obtain polypropylene product.
Relevant technology operating parameter, running condition and polymers analysis results are seen table 1.
Embodiment:
The same Comparative Examples of catalyst preparation process; But after the middle catalyst preparation process of accomplishing Comparative Examples; With the circulation tube of catalyst charge pump as formulation; Continuously the formulation in the preparing tank is extracted out from the bottom, after a T type filter (filter core is individual layer 100 order wire cloths) filters, sent back to preparing tank from top.The internal circulating load of catalyst preparation thing is 600ml/min, cycling time 15min.After accomplishing this catalyzer outer circulation filtration procedure, the same Comparative Examples of the polymerization process of back.
Comparative Examples is seen table 1 with embodiment in the contrast aspect relevant technology operating parameter, running condition and the polymers analysis results.
Table 1
| Project | Comparative Examples | Embodiment |
| Catalyst charge pump discharge pressure MPaG | 4.75 | 4.30 |
| Catalyst charge stability | Feeding line stops up 3 times in 24 hours | Feeding line does not have obstruction in 24 hours |
| Product melting index g/10min (ASTM D1238) | 3.1～3.3 | 3.0～3.1 |
| Product cold xylene solvend wt% (ASTM D5492) | 2.1 | 2.1 |
Can find out in the comparative analysis aspect relevant technology operating parameter, running condition and the polymers analysis results with embodiment by table 1 Comparative Examples; Under PP polymeric articles molecular weight and the essentially identical situation of degree of isotacticity; Adopt catalyst pretreatment method of the present invention to make the catalyst charge pump discharge pressure obviously on the low side; Catalyst charge is stable, does not have and stops up, for the industrial operation of PP polymkeric substance is laid good basis.
Claims (4)
1. a catalyst pretreatment method that is used for catalyst preparation is become paste is characterized in that, this catalyst pretreatment method comprises catalyst preparation jar (1), formulation recycle pump (2); Strainer (3) gets up above-mentioned three devices in series with the material circulation line, forms circulation loop; Described catalyst preparation jar is the container that has the preparation catalyzer of stirring, and the inlet that the top of preparing tank has catalyzer and makes up oil is after process for preparation is accomplished; The catalyst preparation thing is drawn from preparing pot bottom; After the recycle pump supercharging, leach big particle diameter solid impurity wherein with strainer, the catalyst preparation thing sends back to preparing tank through circulation loop from the top of preparing tank; Instantly get together for fun when closing the equipment claimed catalyzer, the catalyzer that comes out from strainer (3) is delivered to the catalyst charge pump on demand.
2. the catalyst pretreatment method that is used for catalyst preparation is become paste according to claim 1 is characterized in that, used formulation recycle pump is spiral pump, peristaltic pump, steam piano, toothed gear pump, surge pump, syringe pump in this pretreatment process; Described strainer is deep bed filter, y-type filter, T type filter.
3. the catalyst pretreatment method that is used for catalyst preparation is become paste according to claim 1; It is characterized in that; Used catalyst preparation thing is meant that hydrocarbon ils, the hydrocarbon fat that is used for catalyst preparation is aliphatic compound, arene compounds or its mixture with the catalyzer paste after hydrocarbon ils and/or the dilution of hydrocarbon fat in this pretreatment process.
4. the catalyst pretreatment method that is used for catalyst preparation is become paste according to claim 1 is characterized in that, used catalyzer is an olefin polymerization catalysis in this pretreatment process.
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| CN2008102248646A CN101724100B (en) | 2008-10-24 | 2008-10-24 | Catalyst pretreatment method |
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| CN2008102248646A CN101724100B (en) | 2008-10-24 | 2008-10-24 | Catalyst pretreatment method |
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|---|---|
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| CN101724100B true CN101724100B (en) | 2012-01-25 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106345372B (en) * | 2015-07-17 | 2019-04-19 | 中国石油化工股份有限公司 | A kind of device of polyolefin catalyst charging |
| CN105170045B (en) * | 2015-07-20 | 2018-02-23 | 神华集团有限责任公司 | Catalyst configuration system, polypropylene production system and catalyst collocation method |
| CN108794670B (en) * | 2017-05-03 | 2020-11-06 | 中国石油天然气股份有限公司 | Improved process for synthesizing polyalphaolefin base oils |
| CN113698513B (en) * | 2020-05-21 | 2023-09-15 | 中国石油化工股份有限公司 | Preparation method and application of catalyst |
| CN114425271A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Discharging metering device for paste materials |
| CN117942863A (en) * | 2024-03-27 | 2024-04-30 | 天津市集散聚合科技有限公司 | Catalyst mixing and filling equipment for polypropylene production and process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1489489A (en) * | 2001-02-02 | 2004-04-14 | ��������ϩ���ɷ�����˾ | Method for dosing catalyst |
| CN1927440A (en) * | 2005-09-09 | 2007-03-14 | 中国石油化工股份有限公司 | Slurry or liquid catalyst feeding device |
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2008
- 2008-10-24 CN CN2008102248646A patent/CN101724100B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1489489A (en) * | 2001-02-02 | 2004-04-14 | ��������ϩ���ɷ�����˾ | Method for dosing catalyst |
| CN1927440A (en) * | 2005-09-09 | 2007-03-14 | 中国石油化工股份有限公司 | Slurry or liquid catalyst feeding device |
Non-Patent Citations (1)
| Title |
|---|
| JP昭58-79533A 1983.05.13 |
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