CN102380340B - Desulfurizer and preparation method thereof - Google Patents
Desulfurizer and preparation method thereof Download PDFInfo
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- CN102380340B CN102380340B CN 201010274016 CN201010274016A CN102380340B CN 102380340 B CN102380340 B CN 102380340B CN 201010274016 CN201010274016 CN 201010274016 CN 201010274016 A CN201010274016 A CN 201010274016A CN 102380340 B CN102380340 B CN 102380340B
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Abstract
The invention provides a desulfurizer, wherein the desulfurizer comprises zinc oxide, sodium carbonate and an adhesive. The invention also provides a preparation method of the desulfurizer; the method comprises forming and activation of a raw material mixture; and the raw material mixture comprises zinc oxide, sodium carbonate and an adhesive. During purification of a propylene crude product, sulfur-containing compounds can be fully removed by using the desulfurizer provided by the invention, and thus a high-purity propylene product with very low sulfur content can prepared.
Description
Technical field
The present invention relates to the preparation method of a kind of desulfurizing agent and this desulfurizing agent.
Background technology
Usually, the liquid hydrocarbon that produces in oil-refining chemical industry (reduced pressure distillation process as usual, catalytic cracking process, heavy oil catalytic cracking process or delay coking process) contains mercaptan, cos (COS), H
2S and CS
2Deng sulfur-containing compound, these sulfur-containing compounds can mix in the organic compound products such as propylene, propane or ethane that prepared by this liquid hydrocarbon, thereby have reduced the quality of the organic compound product of preparation.Therefore, in the described liquid hydrocarbon of employing is prepared with the process of organic compounds product, need to remove these sulfur-containing compounds, to improve the purity of the organic compound product for preparing.Yet, in actual production process, H
2Thereby S can generate the thioether that traditional organic desulfurizing agent is difficult to remove with olefine reaction, and COS and CS
2It itself is also the sulfur-containing compound that adopts traditional organic desulfurizing agent to be difficult to remove.
For this reason, CN 101319149A discloses and a kind of liquid hydrocarbon that delayed coking unit produces has first been carried out pretreatment, then be re-used as the raw material of gas fractionation unit, process to produce the method for propylene, propane, C-4-fraction, wherein, utilize amine liquid to remove the coking liquid hydrocarbon of hydrogen sulfide before carrying out gas fractionation unit, first carry out the soda-wash water wash-out except mercaptan and remove a small amount of water, advance again the COS hydrolytic decomposition pot and carry out desulfurization, then remove again the hydrogen sulfide that hydrolysis produces, then air inlet body fractionating device is processed as raw material.
In above-mentioned patent application, the hydrogen sulfide that produces after the desulfurization of liquid hydrocarbon process COS hydrolytic decomposition pot is to adopt traditional hydrogen sulfide desulphurization agent to remove.Yet these traditional hydrogen sulfide desulphurization agents are difficult to fully remove the hydrogen sulfide in described liquid hydrocarbon, make the sulfur content in the organic compound product of final preparation still higher.
CN 1120970A discloses a kind of novel normal low-temp desulfurization agent, and it comprises that three kinds of following oxide weights form: ZnO 85-95%, Na
2O 0.1-10%, Al
2O
30.1-10%.Although the desulfurizing agent in this patent application has the ability that removes hydrogen sulfide of obvious raising with respect to amine liquid, yet, the Sulfur capacity of this desulfurizing agent is still not high, thereby, this desulfurizing agent still is difficult to prepare the organic compound products such as highly purified propylene for the process that liquid hydrocarbon prepares the organic compound products such as propylene.
Summary of the invention
The present invention adopts existing desulfurizing agent the thick product of propylene to be carried out be difficult to fully remove in the process of purifying the defective of sulfur-containing compound wherein in order to overcome, a kind of new desulfurizing agent and the preparation method of this desulfurizing agent are provided, this desulfurizing agent of employing can fully remove sulfur-containing compound wherein in thick product carries out the process of purifying to propylene, thereby can obtain the very low highly purified propylene product of sulfur content.
The invention provides a kind of desulfurizing agent, wherein, this desulfurizing agent contains zinc oxide, sodium carbonate and adhesive.
The present invention also provides a kind of preparation method of desulfurizing agent, and the method comprises carries out moulding and activation with a kind of raw mix, and described raw mix contains zinc oxide, sodium carbonate and adhesive.
In described desulfurizing agent provided by the invention, owing to containing zinc oxide and sodium carbonate, thereby have very high Sulfur capacity, and then to H
2S and CS
2Has the very strong ability that removes.Therefore, employing described desulfurizing agent provided by the invention can fully remove sulfur-containing compound wherein in thick product carries out the process of purifying to propylene, thereby can prepare the very low highly purified propylene product of sulfur content.In the present invention, described Sulfur capacity refers to the total amount of the sulphur that the Unit Weight desulfurizing agent can effectively remove.
The specific embodiment
Desulfurizing agent according to the present invention contains zinc oxide, sodium carbonate and adhesive.In described desulfurizing agent, there is no particular limitation for the content of described zinc oxide, sodium carbonate and adhesive, yet, for making described desulfurizing agent have higher Sulfur capacity, thereby has the stronger ability that removes sulfur-containing compound, take the gross weight of described desulfurizing agent as benchmark, the content of described zinc oxide is preferably the 65-90 % by weight, more preferably the 70-80 % by weight; The content of described sodium carbonate is preferably the 5-20 % by weight, more preferably the 10-15 % by weight; The content of described adhesive is preferably the 3-20 % by weight, more preferably the 5-15 % by weight.
In described desulfurizing agent, the adhesive in described desulfurizing agent can be the various adhesives that routine is used, for example can be in kaolin, sodium metaaluminate, the sweet soil of sheep and diatomite at least a.In the preferred case, described adhesive is sodium metaaluminate, thereby makes described desulfurizing agent have higher Sulfur capacity.
The present invention also provides a kind of preparation method of desulfurizing agent, and the method comprises carries out moulding and activation with a kind of raw mix, and described raw mix contains zinc oxide, sodium carbonate and adhesive.
In a kind of preferred embodiment, in order further to improve the Sulfur capacity of prepared desulfurizing agent, add zinc carbonate in described raw mix.Described zinc carbonate can play the reaming effect, thereby makes the desulfurizing agent of final preparation have pore volume and the bore dia of increase, and then improves the Sulfur capacity of described desulfurizing agent.
In the process of the described desulfurizing agent of preparation, there is no particular limitation for the addition of described zinc carbonate, yet, Sulfur capacity for the desulfurizing agent that significantly improves final preparation, described raw mix with respect to 100 weight portions, the addition of described zinc carbonate is preferably the 1-15 weight portion, more preferably the 3-12 weight portion.
In the process of the described desulfurizing agent of preparation, there is no particular limitation in the present invention for the method for described moulding, can adopt conventional forming method to implement, and the method for described moulding for example can be extrusion molding.
In the process of the described desulfurizing agent of preparation, the method for described activation can be included under inert gas atmosphere at 120-500 ℃ of lower heat treatment 1-5 hour; In a kind of preferred embodiment, in the situation that added zinc carbonate in the mixture of described zinc oxide, sodium carbonate and adhesive, the method for described activation was included under inert gas atmosphere at 350-450 ℃ of lower heat treatment 1-5 hour.Described heat treatment is by implementing in the environment that the article shaped that obtains after described moulding is positioned over said temperature scope (be 120-500 ℃, be preferably 350-450 ℃).Under above-mentioned activation condition, zinc carbonate decomposes, and generates carbon dioxide and zinc oxide, and described zinc oxide is used for the active component of the described desulfurizing agent of supply.The gas of described inert gas for not reacting with described zinc oxide, sodium carbonate and adhesive under 120-500 ℃.Described inert gas can be in nitrogen, argon gas, helium and neon at least a.
By the following examples invention is described further, but the present invention is not limited only to this.
Embodiment 1
The present embodiment is used for illustrating described desulfurizing agent provided by the invention and preparation method thereof.
The zinc oxide of 67 weight portions, the sodium carbonate of 11 weight portions, the zinc carbonate of 11 weight portions, the sodium metaaluminate of 11 weight portions and appropriate water are mixed; make mixed slurry; then use the double screw extruder extrusion molding; and dry under 120 ℃; activating 2 hours under 380 ℃ under nitrogen protection afterwards; be cooled to afterwards room temperature, thereby obtain desulfurizing agent A1.
Embodiment 2
The present embodiment is used for illustrating described desulfurizing agent provided by the invention and preparation method thereof.
The zinc oxide of 65 weight portions, the sodium carbonate of 14 weight portions, the zinc carbonate of 7 weight portions, the kaolin of 14 weight portions and appropriate water are mixed; make mixed slurry; then use the double screw extruder extrusion molding; and dry under 120 ℃; activating 1.5 hours under 450 ℃ under nitrogen protection afterwards; be cooled to afterwards room temperature, thereby obtain desulfurizing agent A2.
Embodiment 3
The present embodiment is used for illustrating described desulfurizing agent provided by the invention and preparation method thereof.
The zinc oxide of 77 weight portions, the sodium carbonate of 10 weight portions, the zinc carbonate of 3 weight portions, the sweet soil of sheep of 10 weight portions and appropriate water are mixed; make mixed slurry; then use the double screw extruder extrusion molding; and dry under 120 ℃; activating 2.5 hours under 400 ℃ under argon shield afterwards; be cooled to afterwards room temperature, thereby obtain desulfurizing agent A3.
Embodiment 4
The present embodiment is used for illustrating described desulfurizing agent provided by the invention and preparation method thereof.
Prepare desulfurizing agent according to the method for embodiment 1, difference is not use zinc carbonate in the process of preparation desulfurizing agent, thereby obtain desulfurizing agent A4.
Embodiment 5
The present embodiment is used for illustrating described desulfurizing agent provided by the invention and preparation method thereof.
Prepare desulfurizing agent according to the method for embodiment 1, difference is, the consumption of sodium carbonate is 2 weight portions in the process of preparation desulfurizing agent, and the consumption of zinc oxide is 76 weight portions, thereby obtains desulfurizing agent A5.
Embodiment 6
The present embodiment is used for illustrating described desulfurizing agent provided by the invention and preparation method thereof.
Prepare desulfurizing agent according to the method for embodiment 1, difference is, the consumption of sodium carbonate is 25 weight portions in the process of preparation desulfurizing agent, and the consumption of zinc oxide is 53 weight portions, thereby obtains desulfurizing agent A6.
Comparative Examples 1
Prepare desulfurizing agent according to the method for embodiment 1, difference is not use sodium carbonate in the process of preparation desulfurizing agent, and replace described sodium carbonate with the zinc oxide of identical weight, thereby obtain desulfurizing agent D1.
Comparative Examples 2
With the basic zinc carbonate of 160 weight portions 400 ℃ of lower roastings 3 hours, add wherein the water of the sodium metaaluminate of sodium carboxymethylcellulose pyce, 9 weight portions of basic zinc carbonate, 1 weight portion of 13 weight portions and 36 weight portions and mix, then with the mixture that obtains double screw extruder extrusion molding, dry under 100 ℃, then 400 ℃ of lower roastings 3 hours, thereby obtain containing the desulfurizing agent D2 of the aluminium oxide of the sodium oxide molybdena of zinc oxide, 2.81 % by weight of 92.57 % by weight and 4.62 % by weight.
Test case
(1) preparation crude propylene product
The aqueous solution that makes liquid hydrocarbon (forming as shown in table 1) and contain the N methyldiethanol amine of 23 % by weight enters in the absorption tower, the inlet amount of described liquid hydrocarbon is 32 tons/hour, the inlet amount of the aqueous solution of described N methyldiethanol amine is 10 tons/hour, temperature in described absorption tower is 30 ℃, and pressure is 1.2MPa.Then, the NaOH aqueous solution of isolating liquid hydrocarbon and concentration from the bottom on described absorption tower and be 20 % by weight respectively at the bottom of the tower and tower top enter extraction tower, the inlet amount of described liquid hydrocarbon is 35 tons/hour, the inlet amount of the described NaOH aqueous solution is 8 tons/hour, temperature in described extraction tower is 25 ℃, and pressure is 1.2MPa.Afterwards, isolated liquid hydrocarbon is at room temperature washed, the consumption of water is 2 tons/hour.The liquid hydrocarbon that obtains after washing is entered carry out in gas fractionator fractionation, obtaining the thick product of propylene, record according to the method for GB3392-82 the sulfur-containing compound that contains 28ppm in the thick product of described propylene.In the present invention, ppm refers to percentage by weight.
Table 1
(2) preparation hydrolytic reagent
With the alumina support of 100 weight portions (available from Wuhan Hezhong Bio-chemical Manufature Co., Ltd., average pore diameter is 15 nanometers) thorough impregnation is in unsaturated carbonate potassium solution 2 hours, then make absorption have the alumina support of solution of potassium carbonate dry under 100 ℃, with the potash at described alumina support load 15 weight portions.Then, make load have the alumina support of potash to activate 3 hours under the protection at nitrogen under 200 ℃, and be cooled to room temperature, thereby obtain hydrolytic reagent.
(3) purifying of propylene
Make the thick product of propylene that obtains in above-mentioned (1) take weight space velocity as 1.0h
-1Enter successively the desulfurizing agent A1 that is filled with 6 tons fixed bed reactors a (ratio of height to diameter is 4.5), be filled with 8 tons of aluminium oxide fixed bed reactors b (ratio of height to diameter is 4.5), be filled with the fixed bed reactors c (ratio of height to diameter is 4.5) of the hydrolytic reagent that obtains in above-mentioned (2) of 10 tons and be filled with the fixed bed reactors d (ratio of height to diameter is 4.5) of the desulfurizing agent A1 of 10 tons of grams; Temperature in described fixed bed reactors a is 5 ℃, and pressure is 1.2MPa; Temperature in described fixed bed reactors b is 5 ℃, and pressure is 1.2MPa; Temperature in described fixed bed reactors c is 5 ℃, and pressure is 1.2MPa; Temperature in described fixed bed reactors d is 5 ℃, and pressure is 1.2MPa; Collect through the product after described fixed bed reactors d processing as propylene product P1.
Adopt respectively the desulfurizing agent D1-D2 of the desulfurizing agent A2-A6 for preparing in embodiment 2-6 and Comparative Examples 1-2 preparation to replace the desulfurizing agent A1 of preparation in embodiment 1 to carry out the propylene purifying, thereby obtain respectively propylene product P2, P3, P4, P5, P6, PD1 and PD2.
(4) sulfide content in the detection propylene product
Detect respectively the content of the sulfur-containing compound in propylene product P1-P6 and PD1-PD2 according to the method for GB3392-82, its testing result is as shown in table 2 below.
Table 2
| The desulfurizing agent that adopts in purge process | A1 | A2 | A3 | A4 | A5 | A6 | D1 | D2 |
| Propylene product | P1 | P2 | P3 | P4 | P5 | P6 | PD1 | PD2 |
| The content of the sulfur-containing compound in propylene product (ppm) | 1.0 | 1.5 | 1.6 | 2.3 | 1.8 | 2.1 | 4.8 | 3.9 |
Data by table 2 can find out, adopt described desulfurizing agent provided by the invention to carry out desulfurization in the purge process of propylene and in the propylene product that obtains the content of sulfur-containing compound very low, thereby can prepare highly purified propylene product.
Claims (8)
1. a desulfurizing agent, is characterized in that, this desulfurizing agent contains zinc oxide, sodium carbonate and adhesive, wherein, take the gross weight of described desulfurizing agent as benchmark, the content of described zinc oxide is the 65-90 % by weight, the content of described sodium carbonate is the 5-20 % by weight, and the content of described adhesive is the 3-20 % by weight.
2. desulfurizing agent according to claim 1, wherein, take the gross weight of described desulfurizing agent as benchmark, the content of described zinc oxide is the 70-80 % by weight, and the content of described sodium carbonate is the 10-15 % by weight, and the content of described adhesive is the 5-15 % by weight.
3. desulfurizing agent according to claim 1 and 2, wherein, described adhesive is at least a in kaolin, sodium metaaluminate, the sweet soil of sheep and diatomite.
4. the preparation method of the described desulfurizing agent of any one in claim 1-3, is characterized in that, the method comprises carries out moulding and activation with a kind of raw mix, and described raw mix contains zinc oxide, sodium carbonate and adhesive; The method of described activation was included under inert gas atmosphere at 120-500 ℃ of lower heat treatment 1-5 hour.
5. method according to claim 4, wherein, also contain zinc carbonate in described raw mix.
6. method according to claim 5, wherein, with respect to the described raw mix of 100 weight portions, the consumption of described zinc carbonate is the 1-15 weight portion.
7. method according to claim 6, wherein, with respect to the described raw mix of 100 weight portions, the consumption of described zinc carbonate is the 3-12 weight portion.
8. method according to claim 4, wherein, the method for described activation was included under inert gas atmosphere at 350-450 ℃ of lower heat treatment 1-5 hour.
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| CN102703134B (en) * | 2012-05-14 | 2013-12-11 | 太原理工大学 | Method for preparing medium-high temperature gas desulfurizing agent by microwave radiation |
| KR101847319B1 (en) * | 2013-12-17 | 2018-04-09 | 미쓰이 가가쿠 가부시키가이샤 | MOLDED BODY, METHOD FOR PRODUCING SAME, CATALYST FOR α-OLEFIN DIMERIZATION, AND METHOD FOR PRODUCING α-OLEFIN DIMER |
| CN115634713A (en) * | 2022-10-26 | 2023-01-24 | 浙江誉衡环保科技有限公司 | Desulfurization synergist for flue gas desulfurization and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358921A (en) * | 1989-06-07 | 1994-10-25 | Phillips Petroleum Company | Selective removal of hydrogen sulfide over a zinc oxide and silica absorbing composition |
| CN101450302A (en) * | 2008-12-17 | 2009-06-10 | 中国科学院大连化学物理研究所 | C 4 olefin desulfurization absorbent and production method and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86100015B (en) * | 1986-01-06 | 1988-10-05 | 中国石油化工总公司石油化工科学研究院 | Low temp. liquid phase hydrocarbon desulfurizer |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358921A (en) * | 1989-06-07 | 1994-10-25 | Phillips Petroleum Company | Selective removal of hydrogen sulfide over a zinc oxide and silica absorbing composition |
| CN101450302A (en) * | 2008-12-17 | 2009-06-10 | 中国科学院大连化学物理研究所 | C 4 olefin desulfurization absorbent and production method and use thereof |
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Application publication date: 20120321 Assignee: SINOPEC CATALYST CO., LTD. Assignor: Sinopec Corp. Contract record no.: 2014990000622 Denomination of invention: Desulfuration agent and preparation method and application thereof Granted publication date: 20130619 License type: Exclusive License Record date: 20140805 |
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