CN102660319B - Preparation method of ion exchange resin for denitrification of naphtha - Google Patents
Preparation method of ion exchange resin for denitrification of naphtha Download PDFInfo
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- CN102660319B CN102660319B CN2012101668340A CN201210166834A CN102660319B CN 102660319 B CN102660319 B CN 102660319B CN 2012101668340 A CN2012101668340 A CN 2012101668340A CN 201210166834 A CN201210166834 A CN 201210166834A CN 102660319 B CN102660319 B CN 102660319B
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Abstract
The invention provides a preparation method of ion exchange resin for denitrification of naphtha. The preparation method comprises the following steps of: reacting polymerized white balls of acrylic acid series macro-porous cation exchange resin with a trace of chlorobenzoyl chloride to generate acylated white balls with benzoyl chloride functional group, reacting with N,N'-dimethyl ethylene diamine to generate amide, and reacting by adding phosphoric acid to introduce a phosphate group to the benzene ring, so as to obtain a qualified product. By using the ion exchange resin prepared by the method, the alkali denitrification rate and yield of the naphtha can be obviously improved, the resin is easy to elute and regenerate, and the alkaline nitrogen-containing compound is convenient to recover and use.
Description
Technical field
The present invention relates to a kind of method of producing ion exchange resin, particularly a kind of preparation method of naphtha denitrogenation spent ion exchange resin.
Background technology
Nitrogen in naphtha has remarkable impact to activity and the life-span of catalytic reforming unit catalyst, usually can make the catalyst poisoning inactivation, or the stability of oil product is descended, and easily generates gelatinous precipitate.In naphtha, the existence form of nitrogen-containing compound is mainly aniline, pyridine, quinoline and its derivates and pyrroles, indoles, carbazole and derivative thereof; wherein on the nitrogen-atoms of the nitrogen-containing compounds such as phenyl amines, pyridines, quinolines, there are lone pair electrons; there is alkalescent, be called as basic nitrogen compound; The method that removes nitrogen-containing compound from naphtha mainly contains hydrofinishing, acid treating, solvent refining, matching method, absorption method etc.The hydrofining technology advanced person, denitrification effect is good, but can not solve the contradiction that the denitrogenation degree of depth and freezing point are gone up, and equipment investment and operating cost is high, the light stability of refined oil is poor with anti-oxidative stability, on applying, is very restricted.Therefore, lot of domestic and international researcher is sight turning facilities small investment, and operating cost is low non-hydrodenitrogeneration technique again.The main method of non-hydrogenation has: acid treating, solvent refining, matching method are refining and combined method is refining, biological denitrificaion and microwave denitrogenation etc.
At first US4287051 is divided into two parts to viscous oil: heavy oil at the bottom of light viscosity oil and tower, then light viscosity oil is carried out to acid extraction refining, and extraction oil is low sticky high nitrogen oil.Oil at the bottom of the high nitrogen extraction oil of low viscosity and high viscosity tower be in harmonious proportion become can pumping miscella, be pumped to the hydrogen manufacturing of partial oxidation device through miscella.Nitrogenous, sulfur-containing compound is converted into ammonia and hydrogen sulfide in the partial oxidation device, further from hydrogen, reclaims and removes.
CN1088606A is a kind of liquid petroleum product solvent extraction denitrogenation method, total nitrogen, basic nitrogen, mercaptan sulfur and low molecular organic acids in being characterized in removing liquid petroleum product by the liquid phase extracting under normal pressure.The denitrogenation solvent is comprised of alcohol and the dilute alkaline aqueous solution of a kind of Cl-C3, and total nitrogen, basic nitrogen, mercaptan sulfur removal efficiency can reach 50%-80%, and can remove the part low molecular organic acids.
US4332676 and US4332675 adopt gas SO
2, remove basic nitrogen from oil product is arranged.Basic nitrogen and SO
2form complex compound sediment with water, further precipitation and separation and denitrogenation, then utilize heating, inorganic solvent process or the methods such as inert gas purge to SO
2regenerated.
Above patented technology all exist diesel yield low, easily produce in emulsion, oil that a small amount of solvent be mixed with is difficult to separate, extract is difficult for processing, and the problem such as solvent-oil ratio is large, and during operating cost, easily cause secondary pollution; Also there are the problems such as poor selectivity, adsorption capacity is little, denitrification percent is lower.
Summary of the invention
For the deficiencies in the prior art; the inventor has invented a kind of preparation method of naphtha denitrogenation spent ion exchange resin; adopt the polymerization Archon of acrylic acid series large hole cation exchanger resin; react with micro-o-chlorobenzoyl chloride, generate the acidylate Archon with chlorobenzoyl chloride functional group, then with N; N '-dimethyl-ethylenediamine reaction generates acid amides; add again phosphatase reaction, have on phosphate group to phenyl ring, obtain qualified products.
The technical scheme that realizes above-mentioned purpose of the present invention is as follows:
A kind of preparation method of naphtha denitrogenation spent ion exchange resin is provided, comprises the following steps:
1). acylation reaction
The polymerization Archon of acrylic acid type cation exchange resin is added to the dichloroethanes solvent, and the 2-5 that dosage is polymerization Archon quality doubly, is preferably 3 times; Stir 2h under normal temperature, make the abundant swelling of Archon; Then the aluminum trichloride (anhydrous) that adds polymerization Archon mass percent 30-50%, the o-chlorobenzoyl chloride of polymerization Archon mass percent 1-5%, be warmed up to 50-100 ℃, is preferably 80 ℃; Reaction 5-10h, be preferably 8h; Product is washed till without aluminium ion with dichloroethanes, obtains intermediate product 1;
It is the polymerization Archon of ion exchange resin, the polymerization Archon of D151 macroreticular weakly acidic cationic exchange resin of acrylic series or the polymerization Archon of D301 macroreticular weakly base acrylic anionic exchanger resin etc. that the polymerization Archon of described acrylic acid series ion exchange resin can be selected commercially available D113 macropore acidulous acrylic acid.
2). aminating reaction
By step 1) intermediate product 1 and the N that obtain, N '-dimethyl-ethylenediamine 1:1-1:4 in mass ratio adds reactor, under stirring, is warming up to 60-100 ℃, is preferably 80 ℃; Reaction 10-30h, be preferably 24h; Stop reaction, extract mother liquor, obtain intermediate product 2;
3) and phosphatase reaction
By step 2) intermediate product 2 obtained and the phosphoric acid of mass percent concentration 60-85%, be preferably 80% phosphoric acid, 1:1-1:2 adds reactor in mass ratio, under stirring, is warming up to 80-120 ℃, is preferably 100 ℃; Reaction 1-5h, be preferably 4h; Stop reaction, by deionized water, be washed till neutrality, the product obtained is naphtha denitrogenation spent ion exchange resin.
Compared with prior art, the ion exchange resin that prepared by the inventive method has following beneficial effect:
1. the basic nitrogen removal rate of naphtha and yield are all higher, and during operation, required pressure is little, easy and simple to handle.
2. the reaction occurred in resin is reversible reaction fast, and the wash-out of resin and regeneration are easy to carry out; Be convenient to recovery and the utilization of basic nitrogen compound.
3. the method that the catalyst that prepared by application the inventive method carries out the naphtha denitrogenation, easy and other denitrogenation methods combine coupling as acid-alkali refining, solvent refining, adsorption refining etc.
The specific embodiment
Following instance is only to further illustrate the present invention, is not the restriction the scope of protection of the invention.
Embodiment 1:
1). acylation reaction
The polymerization Archon of D113 acrylic acid type cation exchange resin is added to the dichloroethanes solvent, and dosage is 2 times of polymerization Archon quality, under normal temperature, stirs 2h, makes the abundant swelling of Archon; Then the aluminum trichloride (anhydrous) that adds polymerization Archon mass percent concentration 30%, the o-chlorobenzoyl chloride of polymerization Archon mass percent concentration 1%, be warmed up to 50 ℃, reaction 5h, product is washed till without aluminium ion with dichloroethanes, obtains intermediate product 1.
2). aminating reaction
By intermediate product 1 and N, N '-dimethyl-ethylenediamine 1:1 in mass ratio adds reactor, under stirring, is warming up to 60 ℃, and reaction 10h, stop reaction, extracts mother liquor, obtains intermediate product 2.
3) hydrolysis
Phosphoric acid by intermediate product 2 with mass percent concentration 80%, 1:1 adds reactor in mass ratio, under stirring, is warming up to 80 ℃, reaction 4h; Stop reaction, by deionized water, be washed till neutrality, obtain product.Products obtained therefrom is numbered KRB-1.
Embodiment 2
Select the polymerization Archon of D151 macroreticular weakly acidic cationic exchange resin of acrylic series in step 1, the other the same as in Example 1.Products obtained therefrom is numbered KRB-2.
Embodiment 3
Select the polymerization Archon of D301 macroreticular weakly base acrylic anionic exchanger resin in step 1, the other the same as in Example 1.Products obtained therefrom is numbered KRB-3.
Embodiment 4
The aluminum trichloride (anhydrous) that adds polymerization Archon mass percent concentration 50% in step 1, the other the same as in Example 1.Products obtained therefrom is numbered KRB-4.
Embodiment 5
The aluminum trichloride (anhydrous) that adds polymerization Archon mass percent concentration 50% in step 1, the other the same as in Example 2.Products obtained therefrom is numbered KRB-5.
Embodiment 6
The aluminum trichloride (anhydrous) that adds polymerization Archon mass percent concentration 50% in step 1, the other the same as in Example 3.Products obtained therefrom is numbered KRB-6.
Embodiment 7
The o-chlorobenzoyl chloride that adds polymerization Archon mass percent concentration 5% in step 1, the other the same as in Example 1.Products obtained therefrom is numbered KRB-7.
Embodiment 8
The o-chlorobenzoyl chloride that adds polymerization Archon mass percent concentration 5% in step 1, the other the same as in Example 2.Products obtained therefrom is numbered KRB-8.
Embodiment 9
The o-chlorobenzoyl chloride that adds polymerization Archon mass percent concentration 5% in step 1, the other the same as in Example 3.Products obtained therefrom is numbered KRB-9.
Embodiment 10.
The o-chlorobenzoyl chloride that adds polymerization Archon mass percent concentration 5% in step 1, the other the same as in Example 4.Products obtained therefrom is numbered KRB-10.
Embodiment 11.
The o-chlorobenzoyl chloride that adds polymerization Archon mass percent concentration 5% in step 1, the other the same as in Example 5.Products obtained therefrom is numbered KRB-11.
Embodiment 12.
Add the o-chlorobenzoyl chloride of polymerization Archon mass percent concentration 5% in step 1, other is with embodiment 6.Products obtained therefrom is numbered KRB-12.
Embodiment 13.
In step 2, by intermediate product 1 and N, N '-dimethyl-ethylenediamine 1:4 in mass ratio adds reactor, the other the same as in Example 1.Products obtained therefrom is numbered KRB-13.
Embodiment 14
In step 2, by intermediate product 1 and N, N '-dimethyl-ethylenediamine 1:4 in mass ratio adds reactor, the other the same as in Example 2.Products obtained therefrom is numbered KRB-14.
Embodiment 15
In step 2, by intermediate product 1 and N, N '-dimethyl-ethylenediamine 1:4 in mass ratio adds reactor, the other the same as in Example 3.Products obtained therefrom is numbered KRB-15.
Embodiment 16.
In step 2, by intermediate product 1 and N, N '-dimethyl-ethylenediamine 1:4 in mass ratio adds reactor,, the other the same as in Example 4.Products obtained therefrom is numbered KRB-16.
Embodiment 17.
In step 2, by intermediate product 1 and N, N '-dimethyl-ethylenediamine 1:4 in mass ratio adds reactor,, the other the same as in Example 5.Products obtained therefrom is numbered KRB-17.
Embodiment 18.
In step 2, by intermediate product 1 and N, N '-dimethyl-ethylenediamine 1:4 in mass ratio adds reactor,, other is with embodiment 6.Products obtained therefrom is numbered KRB-18.
Embodiment 19.
In step 3 phosphoric acid of intermediate product 2 and mass percent concentration 80% in mass ratio 1:2 add reactor, the other the same as in Example 1.Products obtained therefrom is numbered KRB-19.
Embodiment 20
In step 3 phosphoric acid of intermediate product 2 and mass percent concentration 80% in mass ratio 1:2 add reactor, the other the same as in Example 2.Products obtained therefrom is numbered KRB-20.
Embodiment 21
In step 3 phosphoric acid of intermediate product 2 and mass percent concentration 80% in mass ratio 1:2 add reactor, the other the same as in Example 3.Products obtained therefrom is numbered KRB-21.
Embodiment 22.
In step 3 phosphoric acid of intermediate product 2 and mass percent concentration 80% in mass ratio 1:2 add reactor, the other the same as in Example 4.Products obtained therefrom is numbered KRB-22.
Embodiment 23.
In step 3 phosphoric acid of intermediate product 2 and mass percent concentration 80% in mass ratio 1:2 add reactor, the other the same as in Example 5.Products obtained therefrom is numbered KRB-23.
Embodiment 24.
In step 3 phosphoric acid of intermediate product 2 and mass percent concentration 80% in mass ratio 1:2 add reactor, other is with embodiment 6.Products obtained therefrom is numbered KRB-24.
The test of the SPE method of embodiment 25. naphtha oil:
In the glass column lower end of diameter 7mm, a long 400mm glass cotton pad of jam-pack (processing by deionized water), middle with the high resin of dry method filling 200mm, top is filled in a glass cotton pad again, then, diesel samples is added to the flow velocity with 2ml/min in separatory funnel and crosses post, every 10ml sampling is once analyzed, and measures denitrification percent, the results are shown in Table 1:
The comparison of the test specimen nitrogen removal performance that table 1. different process is made
| Numbering | Denitrification percent % |
| KRB－1 | 85 |
| KRB－2 | 88 |
| KRB－3 | 83 |
| KRB－4 | 81 |
| KRB－5 | 80 |
| KRB－6 | 83 |
| KRB－7 | 91 |
| KRB－8 | 89 |
| KRB－9 | 93 |
| KRB－10 | 82 |
| KRB－11 | 92 |
| KRB－12 | 90 |
| KRB－13 | 90 |
| KRB－14 | 88 |
| KRB－15 | 83 |
| KRB－16 | 83 |
| KRB－17 | 86 |
| KRB－18 | 88 |
| KRB－19 | 83 |
| KRB－20 | 91 |
| KRB－21 | 93 |
| KRB－22 | 90 |
| KRB－23 | 89 |
| KRB－24 | 91 |
| The D001 resin | 74 |
With respect to D001 ion exchange resin, the basic nitrogen removal rate of this patent product naphtha is higher, and during operation, required pressure is little, easy and simple to handle, can be widely used aborning.
Claims (8)
1. the preparation method of a naphtha denitrogenation spent ion exchange resin comprises the following steps:
1). acylation reaction
The polymerization Archon of acrylic acid type cation exchange resin is added to the dichloroethanes solvent, and the 2-5 that the solvent dosage is polymerization Archon quality doubly, stirs 2h under normal temperature, makes the abundant swelling of Archon; Then add the aluminum trichloride (anhydrous) of polymerization Archon mass percent 30-50%, the o-chlorobenzoyl chloride of polymerization Archon mass percent 1-5%, be warmed up to 50-100 ℃, reaction 5-10h, product is washed till without aluminium ion with dichloroethanes, obtains intermediate product 1;
2). aminating reaction
By step 1) intermediate product 1 and the N that obtain, N'-dimethyl-ethylenediamine 1:1-1:4 in mass ratio adds reactor, under stirring, is warming up to 60-100 ℃, and reaction 10-30h, stop reaction, extracts mother liquor, obtains intermediate product 2;
3) and phosphatase reaction
By step 2) intermediate product 2 obtained and the phosphoric acid of mass percent concentration 60-85%, 1:1-1:2 adds reactor in mass ratio, under stirring, be warming up to 80-120 ℃, reaction 1-5h, stop reaction, by deionized water, be washed till neutrality, the product obtained is naphtha denitrogenation spent ion exchange resin.
2. preparation method claimed in claim 1, is characterized in that: step 1) the polymerization Archon of described acrylic acid series ion exchange resin is selected from the polymerization Archon that commercially available D113 macropore acidulous acrylic acid is ion exchange resin, the polymerization Archon of D151 macroreticular weakly acidic cationic exchange resin of acrylic series or the polymerization Archon of D301 macroreticular weakly base acrylic anionic exchanger resin.
3. preparation method claimed in claim 1, is characterized in that: step 1) described polymerization Archon adds the dichloroethanes solvent, and the solvent dosage is 3 times of polymerization Archon quality.
4. preparation method claimed in claim 1, is characterized in that: step 1) acylation reaction of described polymerization Archon and aluminum trichloride (anhydrous), o-chlorobenzoyl chloride, be to be warming up to 80 ℃, reaction 8h.
5. preparation method claimed in claim 1, is characterized in that: step 2) described aminating reaction is to be warming up to 80 ℃ under stirring, reaction 24h.
6. preparation method claimed in claim 1, is characterized in that: step 3) described phosphoric acid is the phosphoric acid that mass percent concentration is 80%.
7. preparation method claimed in claim 1, is characterized in that: step 3) described intermediate product 2 reacts with phosphoric acid, is under stirring, is warming up to 100 ℃, reaction 4h.
8. preparation method claimed in claim 1, is characterized in that, comprises the following steps:
1). acylation reaction
To in the polymerization Archon of acrylic acid type cation exchange resin, add the dichloroethanes solvent, the solvent dosage is 3 times of polymerization Archon quality, under normal temperature, stirs 2h, makes the abundant swelling of Archon; Then add the aluminum trichloride (anhydrous) of polymerization Archon mass percent 30-50%, the o-chlorobenzoyl chloride of polymerization Archon mass percent 1-5%, be warmed up to 80 ℃, reaction 8h, product is washed till without aluminium ion with dichloroethanes, obtains intermediate product 1;
2). aminating reaction
By step 1) intermediate product 1 and the N that obtain, N'-dimethyl-ethylenediamine 1:1-1:4 in mass ratio adds reactor, under stirring, heats up 80 ℃, and reaction 24h, stop reaction, extracts mother liquor, obtains intermediate product 2;
3) and phosphatase reaction
By step 2) intermediate product 2 obtained and the phosphoric acid of mass percent concentration 80%, 1:1-1:2 adds reactor in mass ratio, under stirring, be warming up to 100 ℃, reaction 4h, stop reaction, be washed till neutrality by deionized water, the product obtained is naphtha denitrogenation spent ion exchange resin.
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| CN111285391A (en) * | 2020-03-13 | 2020-06-16 | 北京耀智环保科技有限公司 | Preparation method and device of high-purity rare earth carbonate and ion exchange resin |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4238320A (en) * | 1979-04-19 | 1980-12-09 | Gulf Research & Development Company | Denitrogenation of shale oil |
| CN1583964A (en) * | 2004-05-24 | 2005-02-23 | 山东大学 | Method for removing micro-nitrogenous compound in diesel deeply |
| CN1632063A (en) * | 2004-11-17 | 2005-06-29 | 南京工业大学 | Method for solid phase coordination extraction and removal of basic nitrogen compound from diesel and gasoline |
| CN101229507A (en) * | 2008-02-27 | 2008-07-30 | 南京工业大学 | Benzothiophenes molecular imprinting polymeric adsorbent, preparing method and applications thereof |
| CN101948554A (en) * | 2010-10-09 | 2011-01-19 | 南京大学 | Weak acid cation exchange microballoon resin of magnetic acrylic acid series and synthesis method thereof |
| CN102234352A (en) * | 2011-04-20 | 2011-11-09 | 安徽美佳新材料股份有限公司 | Preparation method of D213 macroporous strong-basic acrylic cation exchange resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7098253B2 (en) * | 2004-05-20 | 2006-08-29 | 3M Innovative Properties Company | Macroporous ion exchange resins |
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2012
- 2012-05-25 CN CN2012101668340A patent/CN102660319B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4238320A (en) * | 1979-04-19 | 1980-12-09 | Gulf Research & Development Company | Denitrogenation of shale oil |
| CN1583964A (en) * | 2004-05-24 | 2005-02-23 | 山东大学 | Method for removing micro-nitrogenous compound in diesel deeply |
| CN1632063A (en) * | 2004-11-17 | 2005-06-29 | 南京工业大学 | Method for solid phase coordination extraction and removal of basic nitrogen compound from diesel and gasoline |
| CN101229507A (en) * | 2008-02-27 | 2008-07-30 | 南京工业大学 | Benzothiophenes molecular imprinting polymeric adsorbent, preparing method and applications thereof |
| CN101948554A (en) * | 2010-10-09 | 2011-01-19 | 南京大学 | Weak acid cation exchange microballoon resin of magnetic acrylic acid series and synthesis method thereof |
| CN102234352A (en) * | 2011-04-20 | 2011-11-09 | 安徽美佳新材料股份有限公司 | Preparation method of D213 macroporous strong-basic acrylic cation exchange resin |
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