阅读说明：本技术 一种改性NaY型分子筛在再生橡胶脱硫过程中的应用 (A kind of application of Modified NaY type molecular sieve in reclaimed rubber sweetening process ) 是由 焦钰 王泽刚 张万明 张�浩 夏禄山 夏齐 古为月 达则晓丽 于 2019-08-29 设计创作，主要内容包括：本发明属于橡胶再生领域,公开了一种改性NaY型分子筛及其应用。本发明的改性NaY型分子筛通过以下方法制备：(1)将NaY分子筛分散于去离子水中搅拌清洗,抽滤,烘干；(2)NaY型分子筛烘干后浸入改性剂中进行改性处理；步骤(2)中改性剂是磺酸、海藻酸盐水溶液、甲基纤维素水溶液、18碳酸、乙烯基硅烷、硅酸乙酯等中的一种或多种；任选的,所述步骤(2)中烘干的NaY分子筛先浸入硝酸铈溶液浸泡后再抽滤,烘干,焙烧后再浸入改性剂中。本发明的改性NaY型分子筛应用于再生橡胶脱硫过程中可以使再生橡胶产品无味,加速橡胶脱硫开链,且所述改性分子筛增加极性小分子在橡胶脱硫过程中的吸附后还能以冲洗-加热的简易方式再生,经济环保。(The invention belongs to rubber regeneration field, a kind of Modified NaY type molecular sieve and its application are disclosed.Modified NaY type molecular sieve of the invention is prepared by the following method: (1) it by NaY molecular sieve disperses in deionized water stirring and washing, filters, drying；(2) it is immersed in modifying agent after the drying of NaY type molecular sieve and is modified processing；Modifying agent is one of sulfonic acid, alginate aqueous solution, methylated cellulose aqueous solution, 18 carbonic acid, vinyl silanes, silester etc. or a variety of in step (2)；Optional, the NaY molecular sieve dried in the step (2) is submerged initially in after cerous nitrate solution impregnates and filters again, dries, immerses in modifying agent again after roasting.Modified NaY type molecular sieve of the invention is applied to reclaimed rubber product can be made tasteless in reclaimed rubber sweetening process, accelerate devulcanization of rubber open chain, and can also be regenerated after absorption of modified molecular screen increase polar micromolecules during devulcanization of rubber with flushing-heating easy means, it is economic and environment-friendly.)

1. a kind of Modified NaY type molecular sieve, which is characterized in that the Modified NaY type molecular sieve is prepared by the following method:

(1) stirring and washing in deionized water is dispersed by NaY molecular sieve, filtered, drying；

(2) it is immersed in modifying agent after the drying of NaY type molecular sieve in step (1) and is modified processing；

Modifying agent is sulfonic acid, alginate aqueous solution, methylated cellulose aqueous solution, 18 carbonic acid, vinyl silicon in the step (2) One of alkane, acyl silanes, hydrosulphonyl silane, chloro silane, silester are a variety of；

Optional, the NaY molecular sieve dried in the step (2) is submerged initially in after cerous nitrate solution impregnates and filters again, dries, roasting It immerses in modifying agent again afterwards.

2. Modified NaY type molecular sieve according to claim 1, which is characterized in that drying is in 110- in the step (1) It is carried out under the conditions of 130 DEG C.

3. Modified NaY type molecular sieve according to claim 1, which is characterized in that the concentration of the cerous nitrate solution is 0.4-0.6 mol/L；Preferably, the NaY molecular sieve is impregnated 8-12 h in cerous nitrate solution and is filtered again, at 110-130 DEG C Under the conditions of dry, under the conditions of 390-410 DEG C roast 1-3 h.

4. Modified NaY type molecular sieve according to claim 1, which is characterized in that in the step (2) modification be by NaY type molecular sieve stirs evenly dispersion reaction after immersing modifying agent or is placed in the reaction of ultrasonic wave pond, then filters, dries, roasts； Preferably, the suction filtration, drying, roasting are that washing filters, in 270-285 DEG C of roasting 1-3 h after drying；Preferably, described to stir Mixing evenly dispersed reaction is in 900-1100 r/min revolving speed, the evenly dispersed reaction 4-8 h of 75-85 DEG C of condition.

5. Modified NaY type molecular sieve according to claim 1, which is characterized in that the NaY type molecular sieve and modifying agent Mass ratio is 1:(35-45).

6. Modified NaY type molecular sieve according to claim 1, which is characterized in that the NaY type molecular sieve molecular formula is Na₇ [(AlO₂)₇(SiO₂)₁₇]·XH₂O, average specific surface area are 550-570 cm²/ g, average grain diameter are 290-310 μm, are in ball Shape, wherein X is greater than zero.

7. Modified NaY type molecular sieve according to claim 1, which is characterized in that seaweed in the alginate aqueous solution The concentration of hydrochlorate is 4-6g/mL, and the concentration of methylcellulose is 2g/mL in the methylated cellulose aqueous solution.

8. Modified NaY type molecular sieve according to claim 1, which is characterized in that the modifying agent medium vinyl silane is HD-E6103, HD-M6103, acyl silanes HD-M2133, hydrosulphonyl silane HD-M4132, HD-M4122, chloro silane are HD-E5132, HD-M5132, silester HD-S132, HD-S140.

9. the application of any one of -8 Modified NaY type molecular sieves according to claim 1, which is characterized in that use the modification Molecular sieve increases absorption of polar micromolecules during devulcanization of rubber.

10. the application of Modified NaY type molecular sieve according to claim 9, which is characterized in that the Modified NaY type molecular sieve Application be mix to put into digester with mass ratio 1:450-550 by modified molecular screen and rubber powder, in desulfurization pressure 2.1- 2.3MPa, desulfurization under the conditions of 255-280 DEG C of desulfurization temperature.

Technical field

The present invention relates to rubber regeneration field, it is specifically related to a kind of Modified NaY type molecular sieve and its application.

Background technique

China or even the whole world are also in rubber sources shortage environment, and waste rubber is unable to natural degradation for a long time, It is black pollution more intractable than plastic pollution (white pollution), therefore, the development and utilization of reclaimed rubber have far reaching significance.

Rubber regeneration mainly with chemical method desulfurization, pay attention to exhaust aftertreatment process, pass through tail gas by reclaimed rubber desulfurization at present Processing unit completes tail gas clean-up.On the one hand, small molecule compound caused by devulcanization of rubber open chain (hydrogen sulfide, sulfur dioxide, Sulfur alcohol compound, thio-ether type compounds, chloride, amide, Benzazole compounds etc.) it will affect the progress of desulphurization reaction.Separately On the one hand, part small molecule is easily absorbed into reclaimed rubber at high temperature, makes reclaimed rubber in use since volatilization generates stimulation Property smell, limits the production and application range of reclaimed rubber.The removing master of small molecule compound during current industrial production To pass through solvent dissolution or activated carbon adsorption.However, temperature is up to 280 DEG C or more during devulcanization of rubber, solvent is volatile, living Property charcoal adsorbance it is minimum, solvent dissolution or active carbon adsorption removing small molecule compound during high temperature desulfurizing effect compared with Difference.

Summary of the invention

The purpose of the invention is to overcome the shortcomings of above-mentioned background technique, a kind of Modified NaY type molecular sieve is provided.This The molecule that invention is strong with hydrophilic ability, reacts with molecular sieve part is promoted by heating stirring or ultrasonic wave, inhales it sufficiently It is attached, then volatilization non-reacted molecules are roasted by Muffle furnace, while promoting group further combined with to reach enhancing molecular sieve pole Property, a greater amount of adsorption effects of polar micromolecules are realized at high temperature under high pressure.

To achieve the object of the present invention, Modified NaY type molecular sieve of the invention is prepared by the following method:

(1) stirring and washing in deionized water is dispersed by NaY molecular sieve, filtered, drying；

(2) it is immersed in modifying agent after the drying of NaY type molecular sieve in step (1) and is modified processing；

Modifying agent is sulfonic acid, alginate aqueous solution, methylated cellulose aqueous solution, 18 carbonic acid, vinyl silicon in the step (2) One of alkane, acyl silanes, hydrosulphonyl silane, chloro silane, silester are a variety of；

Optional, the NaY molecular sieve dried in the step (2) is submerged initially in after cerous nitrate solution impregnates and filters again, dries, roasting It immerses in modifying agent again afterwards.

Further, drying is carried out under the conditions of 110-130 DEG C in the step (1).

Further, the concentration of the cerous nitrate solution is 0.4-0.6 mol/L.

Preferably, the NaY molecular sieve is impregnated 8-12 h in cerous nitrate solution and is filtered again, under the conditions of 110-130 DEG C It dries, 1-3 h is roasted under the conditions of 390-410 DEG C.

Further, modification is to stir evenly dispersion after NaY type molecular sieve is immersed modifying agent in the step (2) It reacts or is placed in the reaction of ultrasonic wave pond, then filter, dry, roast；Preferably, the suction filtration, drying, roasting are that washing is taken out Filter, in 270-285 DEG C of roasting 1-3 h after drying.

Preferably, it is described stir evenly dispersion reaction be in 900-1100 r/min revolving speed, 75-85 DEG C of condition is evenly dispersed React 4-8 h.

It is further preferred that the mass ratio of the NaY type molecular sieve and modifying agent is 1:(35-45).

Preferably, heretofore described NaY type molecular sieve molecular formula is Na₇[(AlO₂)₇(SiO₂)₁₇]·XH₂O, average specific Surface area is 550-570 cm²/ g, average grain diameter is 290-310 μm, spherical in shape, wherein X is greater than zero.

Preferably, the concentration of alginate is 4-6g/mL in the alginate aqueous solution, and the methylcellulose is water-soluble The concentration of methylcellulose is 2g/mL in liquid.

Preferably, the modifying agent medium vinyl silane be HD-E6103, HD-M6103, acyl silanes HD-M2133, Hydrosulphonyl silane is HD-M4132, HD-M4122, and chloro silane is HD-E5132, HD-M5132, silester HD-S132, HD- S140.Aforementioned modifiers can be bought from Qingdao perseverance up to Zhong Cheng Science and Technology Ltd..

The present invention also provides a kind of applications of aforementioned modified NaY type molecular sieve, i.e., are increased using the modified molecular screen Absorption of polar micromolecules during devulcanization of rubber.

Further, the application of the Modified NaY type molecular sieve is by modified molecular screen and rubber powder with mass ratio 1:450- 550 mixing investment digesters, the desulfurization under the conditions of desulfurization pressure 2.1-2.3MPa, 255-280 DEG C of desulfurization temperature.

Modified NaY type molecular sieve of the invention be applied to reclaimed rubber sweetening process in can make reclaimed rubber product without Taste accelerates devulcanization of rubber open chain, and after absorption of modified molecular screen increase polar micromolecules during devulcanization of rubber also It can be regenerated with flushing-heating easy means, it is economic and environment-friendly.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated.Additional aspect and advantage of the invention will be set forth in part in the description, partially will be under Become obvious in the description in face, or practice through the invention is recognized.It is only used to explain this hair it should be appreciated that being described below It is bright, it is not intended to limit the present invention.

Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering Non-exclusionism includes.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic Element.

Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end Value and all integers and score in the range.

Singular includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " any It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.

Indefinite article "an" before element or component of the present invention (goes out the quantitative requirement of element or component with "one" Occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and singular Element or component also include plural form, unless the quantity obviously only refers to singular.

NaY type molecular sieve molecular formula is Na in each embodiment of the present invention₇[(AlO₂)₇(SiO₂)₁₇]·XH₂O, it is average Specific surface area is 560 cm²/ g, average grain diameter is 300 μm, spherical in shape, wherein X is greater than zero.

Moreover, technical characteristic involved in each embodiment of the present invention as long as they do not conflict with each other can To be combined with each other.