CN106496372A

CN106496372A - Bulky grain cross-linked polystyrene resin catalyst and preparation method thereof

Info

Publication number: CN106496372A
Application number: CN201611012547.9A
Authority: CN
Inventors: 徐孝旭; 陈启凡; 冷东斌; 王帅印; 李�瑞
Original assignee: DANDONG MINGZHU SPECIAL TYPE RESIN Co Ltd
Current assignee: DANDONG MINGZHU SPECIAL TYPE RESIN Co Ltd
Priority date: 2016-11-17
Filing date: 2016-11-17
Publication date: 2017-03-15

Abstract

The present patent application provides a kind of bulky grain crosslinked polystyrene catalyst and preparation method thereof.This bulky grain crosslinked polystyrene catalyst be by first swelling, section heats up, soaking zone sulfonating reaction and washing and post processing are prepared repeatedly.The technical program has filled up the technological gap that bulky grain polystyrene bead sulfonation prepares catalyst, many advantages, such as the possessed bed resistance of bulky grain polystyrene resins catalyst is little, handling capacity is strong is represented in actual industry really.

Description

Bulky grain cross-linked polystyrene resin catalyst and preparation method thereof

Technical field

The present application relates to be cross-linked polystyrene resin catalyst and preparation method thereof, more particularly to bulky grain hand over Polystyrene resin catalyst and preparation method thereof.

Background technology

Polystyrene resins catalyst is that styrene and divinylbenzene crosslink copolymerization are bead, then sulfonated prepared.Existing It is quite ripe that the little particle polystyrene bead resin sulfonation of technology prepares catalyst technology, and has been achieved with industrialization amount Produce.But the diversification of the development and application demand with technology, polystyrene resins bulky grainization can have bed resistance because of which Little, handling capacity is strong, easy to loading and unloading, stable performance many advantages, such as, become one new technique of macromolecule chemical industry catalyst industry need Ask.Though Chinese patent CN2010102536937 has been disclosed bulky grain crosslinked polystyrene Archon preparation method, to its sulfonation But suffer defeat after defeat, little particle polystyrene bead resin sulfonation technology cannot be applied, also cannot accordingly be adjusted according to granular size Process to complete the sulfonation of bulky grain polystyrene bead.

Content of the invention

The goal of the invention of the present patent application is to develop new sulfonation technology means and completes bulky grain polystyrene resins and urge Prepared by agent industry, there is provided a kind of bulky grain cross-linked polystyrene resin catalyst and preparation method thereof.The present patent application is provided Bulky grain cross-linked polystyrene resin catalyst technology scheme, its main technical content is：A kind of bulky grain is crosslinked polyphenyl second Olefine resin catalyst, is prepared through following methods by bulky grain crosslinked polystyrene Archon：

1., swelling：Bulky grain crosslinked polystyrene Archon is 1 with the mass ratio of extender：（0.4～0.5）, add extender molten Swell granule crosslinked polystyrene Archon；

2., sulfonating reaction：Add catalyst sulfuric acid silver, then be slowly added the concentrated sulphuric acid that mass fraction is 98%, be warming up to thereafter 75 DEG C, insulation 7.5～8.5 hours, be warming up to thereafter 85 DEG C, insulation 19.5～20.5 hours, then be warming up to 100 DEG C, insulation 14.5 ～15.5 hours；

3., washing and post processing：Distillation recovery dichloroethanes, discharge spent acid, clean remaining two with the sulphuric acid that mass fraction is 70% Ethyl chloride and spent acid, then be washed with deionized resin to effluent in neutrality, the washing be with 25 hours by 100 DEG C of equal prompt drops Cooling washing is warmed to room temperature, 150-250 hours are incubated under 120～155 DEG C of temperature conditionss, finally prepared brown bulky grain Cross-linked polystyrene resin catalyst；

Described extender is dichloroethanes.

The present patent application additionally provides a kind of preparation method of above-mentioned bulky grain polystyrene resins catalyst.

Bulky grain polystyrene resins catalyst and preparation method thereof technical scheme disclosed in the present patent application, is prepared by which Method obtains the bulky grain polystyrene resins catalyst for meeting technical requirements, and has reached excellent catalyst technology and quality Require, filled up the technological gap that bulky grain polystyrene bead sulfonation prepares catalyst, urged bulky grain polystyrene resins The possessed bed resistance of agent is little, handling capacity is strong, easy to loading and unloading, stable performance many advantages, such as obtain in actual industry really Real represents, and can greatly simplify inside reactor structure, can directly fill in fixed bed and tower reactor, be widely used in The fields such as petrochemical industry, fine chemistry industry and pharmaceuticals industry.And adopt skill obtained by the method for sulfonating of the white pearl of little particle polystyrene The bulky grain resin catalyst of art index request, its mass exchange capacity only have 1.32 mmol/g, and volume-exchange capacity only has 0.52 mmol/ml, water content 10%, rate of small round spheres/% 95.5 after mill.

Specific embodiment

Bulky grain cross-linked polystyrene resin catalyst disclosed in the present patent application, is by being crosslinked polyphenyl second to bulky grain Alkene Archon is implemented obtained in sulfonating reaction, and bulky grain crosslinked polystyrene Archon therein is by patent CN2010102536937 Public technology scheme is prepared, and its particle diameter is mainly distributed on 2.0～3.5mm scopes, and its preparation method is：

1., swelling：Extender is added in described bulky grain crosslinked polystyrene Archon, and described extender is dichloroethanes Archon, polystyrene Archon are 1 with the mass ratio of extender：（0.4～0.5）, it is to stir under 45～55 DEG C of temperature conditionss It is swelling to bulky grain crosslinked polystyrene Archon indeformable, about 2～3 hours time；

2., add catalyst sulfuric acid silver, be slow added into 98% concentrated sulphuric acid, start to warm up to 75 DEG C, insulation 7.5～8.5 little When, it is warming up to thereafter 85 DEG C, is incubated 19.5～20.5 hours, then is warming up to 100 DEG C, is incubated 14.5～15.5 hours, to quality Exchange capacity is more than 4.5mmol/g（Dry state）When terminating reaction；

3., washing and post processing：Distillation recovery dichloroethanes, discharge spent acid, clean remaining two with the sulphuric acid that mass fraction is 70% Ethyl chloride and spent acid, are washed with deionized resin, until effluent is in neutrality, the washing 25 hours makes bead flawless, protects Final product quality is demonstrate,proved；Room temperature is cooled to by 100 DEG C of average rates in the washing of 25 hours, then at 120～155 DEG C of temperature strip 150-250 hours are incubated under part, finally prepared brown bulky grain cross-linked polystyrene resin catalyst, will be easily de- in catalyst The horizontal acid groups that fall are anticipated, to avoid which from affecting the service life of catalyst and increase, to equipment corrosion, to realize activity Group is stablized.

The technical requirements that product fullys meet catalyst high-quality performance are prepared, table 1 below is referred to, 1# samples therein The preparation process condition of product is：Bulky grain polystyrene Archon is 1 with the mass ratio that feeds intake of extender dichloroethanes:0.45, molten The swollen time is 2.5h, in 75 DEG C, insulation 8h, is warming up to thereafter 85 DEG C, insulation 20h, is finally warming up to 100 DEG C, insulation 15h；2# The preparation process condition of sample is：Bulky grain polystyrene Archon is 1 with the mass ratio that feeds intake of extender dichloroethanes:0.4, molten The swollen time is 2h, in 75 DEG C, insulation 7.5h, is warming up to thereafter 85 DEG C, insulation 19.5h, is finally warming up to 100 DEG C, insulation 14.5h；The preparation process condition of 3# samples is：Bulky grain polystyrene Archon with the mass ratio that feeds intake of extender dichloroethanes is 1:0.5, swelling time is 3h, 75 DEG C, insulation 8.5h, be warming up to thereafter 85 DEG C, insulation 20.5h, be finally warming up to 100 DEG C, Insulation 15.5h；

Parameter name	1#	2#	3#	Averagely
					Mass exchange capacity/mmol/g	4.55	4.59	4.56	4.57
Volume-exchange capacity/mmol/ml	2.38	2.34	2.33	2.35
					Water content/%	55	53	53	54
Wet apparent density/g/ml	0.82	0.83	0.83	0.83
					Wet true density/g/ml	1.22	1.28	1.24	1.25
Rate of small round spheres/% after mill	97.6	95.2	96.7	96.5
					Specific surface area/m²/g	29.8	29.2	29.6	29.5
Grade is evaluated	Excellent	Excellent	Excellent	Excellent

Product quality reach excellent, circle percentage of damage less.And adopt obtained by the method for sulfonating of the white pearl of little particle polystyrene Bulky grain resin catalyst, its mass exchange capacity only have 1.32 mmol/g, volume-exchange capacity only have 0.52 mmol/ Ml, water content 10%, rate of small round spheres/% 95.5 after mill.

Claims

1. a kind of bulky grain cross-linked polystyrene resin catalyst, it is characterised in that the catalyst is by bulky grain crosslinked polystyrene Archon is prepared through following methods：

Described extender is dichloroethanes.

2. bulky grain cross-linked polystyrene resin catalyst according to claim 1, it is characterised in that particle diameter is mainly distributed In 2.0～3.5mm.

3. bulky grain cross-linked polystyrene resin catalyst according to claim 1, it is characterised in that bulky grain polyphenyl second Alkene Archon is 1 with the mass ratio that feeds intake of extender dichloroethanes:0.45, swelling time is 2.5h, in sulfonating reaction, protects at 75 DEG C Warm 8h, is warming up to thereafter 85 DEG C of insulation 20h, is finally warming up to 100 DEG C of insulation 15h.

4. bulky grain cross-linked polystyrene resin catalyst according to claim 1, it is characterised in that bulky grain polyphenyl second Alkene Archon is 1 with the mass ratio that feeds intake of extender dichloroethanes:0.4, swelling time is 2h, in sulfonating reaction, is incubated at 75 DEG C 7.5h, is warming up to thereafter 85 DEG C of insulation 19.5h, is finally warming up to 100 DEG C of insulation 14.5h.

5. bulky grain cross-linked polystyrene resin catalyst according to claim 1, it is characterised in that bulky grain polyphenyl second Alkene Archon is 1 with the mass ratio that feeds intake of extender dichloroethanes:0.5, swelling time is 3h, in sulfonating reaction, 75 DEG C of insulations 8.5h, is warming up to thereafter 85 DEG C of insulation 20.5h, is finally warming up to 100 DEG C of insulation 15.5h.

6. in a kind of claim 1 to 5 one of arbitrarily described in bulky grain polystyrene resins catalyst preparation method.