CN102260359B - Method for preparing chromium silica gel catalyst carrier with high specific surface area and large pore volume - Google Patents
Method for preparing chromium silica gel catalyst carrier with high specific surface area and large pore volume Download PDFInfo
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- CN102260359B CN102260359B CN 201110001262 CN201110001262A CN102260359B CN 102260359 B CN102260359 B CN 102260359B CN 201110001262 CN201110001262 CN 201110001262 CN 201110001262 A CN201110001262 A CN 201110001262A CN 102260359 B CN102260359 B CN 102260359B
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Abstract
The invention relates to a silica gel catalyst carrier, in particular to a method for preparing a chromium silica gel catalyst carrier with high specific surface area and large pore volume for a polyethylene catalyst. The chromium silica gel catalyst carrier with high specific surface area and large pore volume has the specific surface area of 350-650m<2>/g, the pore volume of 2-2.8ml/g and the Cr content of 0.5-1.5 percent. The preparation method comprises the following steps of: quickly mixing 10 to 25 weight percent sodium silicate solution and 15 to 35 weight percent sulfuric acid solution in a mixer for reaction to obtain rubber, ageing, washing with water, removing a rubber brick, performing acid leaching, washing with water until the PH is 6-9, filtering off water, performing reflux distillation on a special distillation reactor, performing liquid-solid separation, filtering, drying, crushing, grading airflow, loading chromium, and performing surface modification to obtain the silica gel catalyst carrier.
Description
Technical field
The present invention relates to a kind of silica gel catalyst agent carrier, especially relating to a kind of high-specific surface area, large pore volume chromium that is applicable to that polyethylene catalysts is used is the preparation method of silica-gel carrier.
Background of invention
Silica gel has special pore structure, and big specific surface area and good thermostability are widely used in each industrial circles such as sorbent material, siccative, thickening material, matting agent and support of the catalyst.In recent years, polythene material has become the national economy necessary part, and obtains swift and violent development, and poly production method has vapor phase process, slurry process and three kinds of production technique of solution method.Wherein Unipol polyolefin process route is because reduced investment, advantage such as flow process is short, working cost is low have occupied dominant position gradually in polyolefin industry for this, and the support of the catalyst of this technology is exactly the amorphous silica gel of modification.
Nowadays, in the vinyon (PE) of widespread use, high density polyethylene(HDPE) (HDPE) has been in the world main PE type, and the about high density polyethylene(HDPE) product 40% or more in the whole world is with phillips catalyst plant production, and this catalyzer by the silica gel load chromic salts after a year activated titanium obtain.Since nineteen fifty-one, this catalyzer was found, research had determined that the pore structure of silica gel can influence whole catalytic process.Say that in principle the specific surface area that increases catalyzer can increase its reactive behavior, but single increase specific surface area is not enough, because silica gel also must have friability, because after polyreaction begins, polymkeric substance stops up pore immediately, catalyzer could continue to keep active after this moment, must break, otherwise polyreaction will be ended, so have only large pore volume silica gel just to have enough fragility, in polyreaction, can decompose fully, Here it is, and generally the pore structure of approval is to the influence of catalyst reaction activity in recent years, and it can control the size of molecular weight of polymer.
When traditional method prepared silica gel, specific surface was big, and pore volume is just little.Otherwise pore volume is big, and specific surface is again little, and the two is conflicting.Therefore must prepare the requirement of satisfying olefinic polyreaction with new method.
For this reason, each major company of the world researches and develops the new silica-gel carrier of manufacturing from different angles and field, make it have high specific surface area simultaneously, has big pore volume again, as: W.R.Grace, Phillips oil company, Davison chemical company, SCM chemical companies etc., ZL200410039492.1 has at large enumerated the various processing methodes of external production polyolefin catalyst carrier.
W.R.Grace.Co-conn company is one of major vendor of carrier for olefin polymerization catalyst produced in USA, discloses the manufacture method of two kinds of silica-gel carriers, and the first takes to reduce SiO
2Solubleness or the auxiliary agent of solvation, make SiO
2In the water-sol system of preparation, reduce SiO
2Solubleness and separate out into hydrogel, then through aging, washing, dry and roasting makes SiO
2Finished product, said auxiliary agent are ammonia, monohydroxy-alcohol, dibasic alcohol, ketone and salt.They can reduce the solution electric constant in the water-sol system, thereby make SiO
2Separate out into gel, these auxiliary agents are evenly dispersed in and occupy certain space in the gel, washing, drying and roasting and be removed, and the silica-gel carrier specific surface area of production is 300～400m
2/ g, pore volume 1.2～2.8ml/g.
Disclosed other method is azeotropic distn.The silicon gel that makes after the washing removal of impurities, is added C
5～C
6Alcohol, as the eleventh of the twelve Earthly Branches alcohol, hexanol or their mixture, remove water in the silicon gel by component distillation, obtain xerogel, 450 ℃～700 ℃ roastings make product, its physical index is: pore volume 2.0～2.5ml/g, specific surface area 420～550m
2/ g, bulk density 1.8～2.5g/ml.
Thereafter Grace company has improved azeotropic distn again.Mainly be to have selected some more suitably organic compound, as the compound of alcohol ether, pure ether-ether and so on.As oxyethyl group vinyl acetic monomer, tert.-butoxy propyl alcohol, Methoxy acetic acid propyl ester, the pure and mild ethoxyl ethyl propionate of n-butoxy etc.Carry out component distillation with these organic compound, to scheme to have improved the performance of carrier.
The Phillips oil company discloses many patents earlier, and azeotropic distillation technology has been discussed, and has selected boiling point than higher organic solvent, thinks C
5～C
6Alcohol be advisable, as 3 monomethyl butanols, positive the eleventh of the twelve Earthly Branches alcohol etc. have made the silica-gel carrier of large pore volume, high-specific surface area.
In addition, also studied freezing reaming method abroad, fused salt reaming method, supercritical drying etc.China has just begun to carry out the production domesticization research of polyolefine with silica-gel carrier as far back as the eighties, as the development of Qingdao Haiyang chemical industry group to 955 silica gel, Sinopec institute, Tianjin chemical research institute and many universities etc., number of research projects has been done to the polyolefine silica-gel carrier by many units, and many articles and patent have been delivered, but the polyolefine silica-gel carrier of China still relies on import so far, the enterprise that the unique family of China produces polyethylene catalysts also is the silica-gel carrier raw material that depends on import, carries titanium and produces polyethylene catalysts.
The preparation method that high-specific surface area, the large pore volume of our company's invention carries chrome-silicon glue support of the catalyst has compared many innovations with the preparation method of home and overseas.The first is in gross porosity glue preparation, and we have increased the acidleach removal of impurities and add the urea auxiliary agent in wash water, is conducive to removing and reaming of moisture in the silica gel hole; It two is the organic compound that carry out component distillation, and external that select is high boiling C
5Above alcohol or ester are C and we select
2～C
5Low boiling ester and alcohol, not only reduced boiling temperature, saved energy consumption widely, and reduced soltion viscosity, make the easier dispersion of silica gel product.The 3rd is metal ester class or the alkanes tensio-active agent that we have added high molecular in drying process, and it not only is conducive to the modification of pore structure, has also eliminated interparticle static, has improved surface property.The 4th is that the external chromium acetate-toluene solution that adopts mostly carries chromium, and what we adopted is that chromium acetate-acetum or chromium acetate-ethanolic soln carry chromium.
Can then further specify the present invention by concrete enforcement:
Embodiment 1
With 20 ± 0.5% (wt) sodium silicate solution for preparing and 30 ± 0.5% (wt) sulphuric acid soln for preparing, by weight: the ratio of sodium silicate solution/sulphuric acid soln=5.555, squeeze in the mixing reactor with pump respectively, blend pressure is 0.36 ± 0.02mpa, the reaction mixture temperature is 30～40 ℃, mixed hydrogel is put into acidproof groove, under 35 ± 5 ℃ of temperature, leave standstill aging gelling after 40 hours, cut into the piece glue about 4cm, put into the wash water groove, wash, the hot water temperature is 50～60 ℃, the silica gel that washing obtains to about the pH7 soaked 12 hours with 3.5% Hcl, used 40～50 ℃ of hot washes to more than the pH6 again, added 0.05% urea and soaked and obtain refining silica gel after 4 hours; To make with extra care silica gel soaked 8 hours with the toluene solution that contains Cr1.0% (wt), filter, to carry chrome-silicon glue again and put into the jacket reactor that band stirs, add positive butyl ester and carry out component distillation, after silica gel after the distillation carries out 100 ℃ of vacuum-dryings, the silane of adding 2% carries out modification to be handled, and then pulverizes with air classification and obtains D
50102 μ m, specific surface area 502m2/g (BET), year chrome-silicon glue carrier finished product of pore volume 2.5ml/g.
Embodiment 2
Except following difference, all the other are identical with embodiment 1;
(1) HNO is adopted in acidleach
3, concentration 3.6%;
(2) concentration of adding urea is 1%;
(3) the Cr concentration of carrying chromium is 1.2% acetum;
(4) replace silane modifier with tetrabutyl titanate, add-on is 1.5%.
The index of carrying chrome-silicon glue carrier that obtains is: D
5094 μ m, specific surface area 490m
2/ g (BET), pore volume 2.38ml/g.
Embodiment 3
Except following difference, all the other are identical with embodiment 1;
(1) acidleach Hcl 3.2%, HNO
33.2% mixing solutions;
(2) the Cr concentration of carrying chromium is 0.85% ethanolic soln;
The index of carrying chrome-silicon glue carrier that obtains is: D
50100.5 μ m, specific surface area 510m
2/ g (BET), pore volume 2.52ml/g.
Embodiment 4
Except following difference, all the other are identical with embodiment 1;
(1) acidleach Hcl 3.0%+HNO
33.0% mixing solutions;
(2) the Cr concentration of carrying chromium is 0.95% butanol solution;
(3) organic compound of component distillation is the oxyethyl group vinyl acetic monomer;
The index of carrying chrome-silicon glue carrier that obtains is: D
5098 μ m, specific surface area 495m
2/ g (BET), pore volume 2.43ml/g.
Embodiment 5
Except following difference, all the other are identical with embodiment 1;
(1) acidleach Hcl 3.0%+HNO
33.0% mixing solutions;
(2) the Cr concentration of carrying chromium is 1% isobutanol solution;
(3) organic compound of component distillation is ethyl acetate;
The index of carrying chrome-silicon glue carrier that obtains is: D
5089 μ m, specific surface area 484m
2/ g (BET), pore volume 2.35ml/g.
Embodiment 6
Except following difference, all the other are identical with embodiment 1;
(1) acidleach Hcl 3.5%+HNO
32.5% mixing solutions;
(2) the Cr concentration of carrying chromium is 1% propanol solution;
(3) organic compound of component distillation is isopropylcarbinol;
The index of carrying chrome-silicon glue carrier that obtains is: D
5094 μ m, specific surface area 490m
2/ g (BET), pore volume 2.49ml/g.
Claims (6)
1. a high-specific surface area, large pore volume chromium are the preparation method of silica gel catalyst agent carrier, and the product that described method obtains is that specific surface area is 350 ~ 650m
2/ g, chromium content are that 0.5 ~ 1.5% high-specific surface area, large pore volume chromium are the silica gel catalyst agent carrier, it is characterized in that the pore volume of product is 2.35 ~ 2.8 ml/g, are applicable to the silica gel catalyst agent carrier of for olefines polymerization.
2. according to claim 1, a kind of high-specific surface area, large pore volume chromium are the preparation method of silica gel catalyst agent carrier, it is characterized in that the thick glue that will make uses mineral acid again: acidleach is carried out in a kind of or two kinds of mixing in hydrochloric acid, the nitric acid, leaching time is 4 ~ 24 hours, temperature is 25 ~ 80 ℃, and concentration is 0.5 ~ 5%, after the acidleach with 30 ~ 60 ℃ be washed to more than the pH6.5, and in wash water, add 0.01 ~ 0.1% urea and soak after 1 ~ 6 hour, filter out water and obtain refining silica gel.
3. according to claim 1, a kind of high-specific surface area, large pore volume chromium are the preparation method of silica gel catalyst agent carrier, it is characterized in that the refining silica gel that claim 2 makes is inserted in the stirring distillation reactor, add C
2~ C
5Organic solvent, this organic solvent is C
2~ C
5Alcohol or ester, carry out component distillation and handle.
4. according to claim 1, a kind of high-specific surface area, large pore volume chromium are the preparation method of silica gel catalyst agent carrier, it is characterized in that the silica gel that claim 3 is made adds tensio-active agent, this tensio-active agent is a kind of in tetrabutyl titanate or the silane, consumption 0.5 ~ 3% carries out the silica gel particle surface modification and eliminates static.
5. according to claim 1, a kind of high-specific surface area, large pore volume chromium are the preparation method of silica gel catalyst agent carrier, it is characterized in that silica gel that claim 4 makes is pulverized and air classification obtains D
50The silica gel catalyst agent carrier of 50 ~ 120 μ m.
6. according to claim 1, a kind of high-specific surface area, large pore volume chromium are the preparation method of silica gel catalyst agent carrier, the chromium that carries that it is characterized in that silica gel is handled, chromic salts or chromic oxide are dissolved in the organic solvent, chromium concn is 0.5 ~ 1.5%, its organic solvent is: any in toluene, ethanol, propyl alcohol, butanols, the acetic acid, silica gel was flooded 4 ~ 20 hours, and filtration drying namely obtains high-specific surface area, large pore volume chromium-based catalysts carrier.
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| CN107649111A (en) * | 2017-11-14 | 2018-02-02 | 东莞市鑫益电子科技有限公司 | A kind of preparation method of modified silica-gel |
| CN110237837B (en) * | 2018-05-30 | 2022-04-08 | 广州凌玮科技股份有限公司 | Preparation method of fluidized bed denitration catalyst |
| CN113248639A (en) * | 2021-06-01 | 2021-08-13 | 上海弘岸化工有限公司 | Silica gel supported polyolefin catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522958A (en) * | 2003-02-21 | 2004-08-25 | 青岛海洋化工有限公司 | Process for manufacturing macroreticular spherical silica gel |
| CN1858072A (en) * | 2005-05-08 | 2006-11-08 | 上海纳川化工有限公司 | Process for preparing titanium odified supported chromium catalyst and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522958A (en) * | 2003-02-21 | 2004-08-25 | 青岛海洋化工有限公司 | Process for manufacturing macroreticular spherical silica gel |
| CN1858072A (en) * | 2005-05-08 | 2006-11-08 | 上海纳川化工有限公司 | Process for preparing titanium odified supported chromium catalyst and its use |
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Effective date of registration: 20170801 Address after: 100041 Shijingshan District Xing Xing street, building No. 30, building 7, floor 8,, 701 Co-patentee after: Shanghai Haiyuan Chemical Science and Technology Co., Ltd. Patentee after: Beijing Saideli Technology Co., Ltd. Co-patentee after: Shanghai Tonghui Chemical Co., Ltd. Address before: 201407 Shanghai city Fengxian District Qianqiao fengtuo Highway No. 3403 Co-patentee before: Shanghai Tonghui Chemical Co., Ltd. Patentee before: Shanghai Haiyuan Chemical Science and Technology Co., Ltd. |
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