CN100344363C - Hydrochloric sorbent, and preparation mehtod - Google Patents
Hydrochloric sorbent, and preparation mehtod Download PDFInfo
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- CN100344363C CN100344363C CNB2004101028068A CN200410102806A CN100344363C CN 100344363 C CN100344363 C CN 100344363C CN B2004101028068 A CNB2004101028068 A CN B2004101028068A CN 200410102806 A CN200410102806 A CN 200410102806A CN 100344363 C CN100344363 C CN 100344363C
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Abstract
The present invention relates to an adsorbent used for adsorbing chlorine hydride impurities in gas hydrocarbon or liquid hydrocarbon. The adsorbent comprises the following components proportioned by mass: 25% to 80% of aluminum oxide, 1% to 60% of filling agent and 5% to 65% of metal oxide, wherein the filling agent is selected from argil or bentonite, and the metal oxide is selected from zinc oxide or magnesium oxide or sodium oxide. The adsorbent can further contain 0.3% to 0.5% of manganese oxide proportioned by mass. The adsorbent is used for adsorbing chlorine hydride in gas hydrocarbon or liquid hydrocarbon under low temperature, and has high chlorine adsorbing capacity.
Description
Technical field
The present invention is a kind of chloride absorbent and preparation method, specifically, is can adsorb hydrogen chloride from gaseous state or liquid hydrocarbon under a kind of low temperature, thereby removes the adsorbent of the hydrogen chloride that contains in the hydrocarbons.
Background technology
At present, the catalyst that uses in the Industrial Catalysis reformer all is to think that aluminium oxide is carrier, the catalyst of carried noble metal platinum.For improving the acidity of this type of catalyst, need on carrier, to introduce an amount of chlorine.In the catalyst runs process, chlorine can run off gradually.Be the acidity of maintenance catalyst, need the constantly water and the chlorine of injection trace in reforming system, control water chloride balance, thereby in the generation hydrogen of reforming, can contain the HCl of trace so that catalyst keeps suitable acidity.This hydrogen that contains micro-HCl can bring many adverse influences when supplying with the downstream unit use.Secondly at first, HCl can cause the corrosion of upstream device, if having the nitrogen of trace in the raw material of downstream unit, will generate ammonium chloride, thereby causes cooling device to stop up, recycle compressor enters the mouth frequent incrustation, influences unit normal run.In addition, the HCl of trace can be caused the acidity of catalyst to change by the absorption of the catalyst in the downstream unit, influences the normal performance of catalyst.Therefore, industrial HCl in the reformation hydrogen will being removed is to eliminate its influence.
Existing industrial dechlorination method commonly used has alkali wash and antichlor method, and the spy opens clear 58-58135 and removes hydrogen chloride in the reformation hydrogen with alkali cleaning at normal temperatures.This method is to utilize in the alkali and HCl, and dechlorination speed is fast, and is effective.But alkali wash needs a series of equipment, as equipment such as caustic wash tower, alkali lye storage tank, circulating pump, complex operation.By contrast, it is more economical effective that the antichlor method seems, this method is than traditional alkali wash, and outstanding advantage is that equipment and running cost are low.Dechlorinating process only needs the fixed container of a filling chloride absorbent to get final product, and investment cost and running cost are starkly lower than other dechlorination methods.
The preparation chloride absorbent is that the component selected for use of antichlor is more, use zinc oxide and alkali formula calcium compound to prepare chloride absorbent as US3935259, this adsorbent need use under higher temperature, serviceability temperature generally is higher than 60 ℃, therefore heater must be arranged, increase the energy consumption of adsorption operations.US4374654 uses the adsorbent that contains activated alumina and molecular sieve to remove hydrogen chloride, and activated alumina average molecular sieve price is lower, but the adsorption capacity of hydrogen chloride is also low.Though the adsorption capacity of molecular sieve is high, price is also much higher.
US4639259 adds the appropriate bases metallic compound and makes adsorbent in aluminium oxide, wherein the content of alkaline-earth metal is 0.5～45 weight %.This adsorbent can be reduced to hydrogen chloride in gas content below the 1ppm, and the chlorosity of adsorbent is in 10～20 weight % scopes.
CN1081936A discloses a kind of adsorbent that removes de-chlorine hydride, comprises the alkali metal oxide of at least 5 weight % that calculate with respect to alumina weight in this adsorbent, with the activity of accelerating oxidation aluminium.Its preparation method is the carboxylate with water-soluble alkali, as the sodium acetate impregnated alumina, obtains adsorbent 300～500 ℃ of heating then.
CN1079415A discloses a kind of chloride absorbent and preparation method thereof, can remove the hydrogen chloride impurity in gas or the liquid hydrocarbon.This adsorbent contains the carbonate of gama-alumina and alkali metal or alkaline-earth metal, and wherein the content of alkali metal or alkaline-earth metal accounts for 1～16 weight % of adsorbent total amount.The ability that this agent removes hydrogen chloride is stronger, hydrogen chloride impurity content in gas or the liquid hydrocarbon can be reduced to below the 0.5ppm (weight) the penetrating chlorosity and can reach 25 weight % of adsorbent.
The cost of material that the method for preparing adsorbent is selected for use is all higher, therefore cause the adsorbent cost higher, but the adsorption capacity of hydrogen chloride can not improve a lot.
Summary of the invention
The purpose of this invention is to provide a kind of chloride absorbent, this adsorbent raw material is easy to get, with low cost, the hydrogen chloride adsorption capacity is stronger.
Chloride absorbent provided by the invention, comprise the aluminium oxide of 25～80 quality %, the filler of 1～60 quality % and the metal oxide of 5～65 quality %, described filler is selected from carclazyte or bentonite, and metal oxide is selected from zinc oxide, magnesia or sodium oxide molybdena.
The present invention adopts aluminium oxide, has the filler and the preparation of metal oxides adsorbent of bigger serface, has not only reduced the cost of adsorbent, has also increased the absorption chlorosity amount of adsorbent, and the performance of adsorbent is further enhanced.Use the adsorbent of the present invention's preparation, the hydrogen chloride content in gas or the liquid hydrocarbon can be reduced to below the 0.5ppm, the penetrating chlorosity and can reach 34 quality % of antichlor.
The specific embodiment
In the adsorbent of the present invention, the filler of selecting for use is cheap, and has bigger specific area, therefore can improve the absorption chlorosity amount of adsorbent, metal oxide meta-alkalescence in the adsorbent in helping and the acidity of hydrogen chloride, and improves the adsorption capacity of activated alumina.
Filler is selected from carclazyte or bentonite described in the adsorbent of the present invention.When filler was selected from carclazyte, its content was 10～40 quality %; When filler was selected from bentonite, its content was 1～15 quality %.Described carclazyte or bentonite can be the products of any specification.
Also further contain 0.3～5.0 quality %, the manganese oxide of preferred 0.5～3.0 quality % in the adsorbent of the present invention.The manganese oxide that adds is an auxiliary agent, can interact with the metal oxide in the adsorbent, improves the adsorption capacity of adsorbent.
Aluminium oxide in the adsorbent can not only increase the intensity of absorption, also has certain adsorption activity, and preferred aluminium oxide is a gama-alumina.
The shape of adsorbent can be stripe shape, ball-type or sheet, preferred stripe shape.
Preparation of adsorbent method provided by the invention comprises that the precursor with aluminium hydroxide, filler and metal oxide or metal oxide mixes aftershaping, dry then, roasting, and described metal oxide is zinc oxide, magnesia or sodium oxide molybdena.
Among the above-mentioned adsorbent preparation method, the precursor with aluminium hydroxide, filler and metal oxide or metal oxide is mixed and made into mixture earlier, and then carries out moulding.Also further comprise manganese oxide or its precursor in the described mixture.
The precursor of described metal oxide or manganese oxide is selected from the hydroxide or the water soluble salt of zinc, magnesium, sodium or manganese.The acetate of the preferred zinc of described water soluble salt, magnesium, sodium or manganese.
Can change into the aluminium hydroxide of gama-alumina after the preferred roasting of the aluminium hydroxide that uses in the described method, as boehmite or boehmite.Filler is selected from carclazyte or bentonite.
The moulding of adsorbent of the present invention can be adopted and mix pinching bar method, infusion process, rolling ball method or pressed disc method, preferred extruded moulding method.The method of extruded moulding is to prepare the dried even mixture of making that is mixed of the used various raw materials of adsorbent earlier, adds an amount of peptizing agent and water then in mixture, also can add extrusion aid, as the sesbania powder, mixes and pinches evenly, afterwards extruded moulding.Extrudate is left standstill a period of time, and preferred 2～8 hours, dry then, roasting promptly made adsorbent.Preferred 50～130 ℃ of described baking temperature, preferred 2～6 hours of time, preferred 400～650 ℃ of sintering temperature, preferred 2～6 hours of time.
Adsorbent of the present invention both can be used for removing hydrogen chloride in gas, can be used for removing the hydrogen chloride in the liquid hydrocarbon again.The serviceability temperature of adsorbent is 0～100 ℃.
Below by example in detail the present invention, but the present invention is not limited to this.
Adsorbent penetrates the assay method of chlorosity and is in the example: with the adsorbent porphyrize, the particles of getting 10 grams, the 0.25～0.50mm internal diameter of packing into is in 6 millimeters the quartz glass tube, under 20 ℃, 1000 hours-1 condition of volume space velocity, feed the nitrogen that contains 50ppm hydrogen chloride, the content of hydrogen chloride in the gas of the adsorbent bed exit of continuous detecting, when the exit gas hydrogen chloride content is higher than 0.5ppm, stop reaction.Analyze the content of hydrogen chloride in the adsorbent, this value is the chlorosity that penetrates of tested adsorbent.
Example 1～3
The different oxides of following case expedition are to the influence of performance of the adsorbent.
(Shandong Aluminum Plant produces to get 40 gram boehmites, alumina content is 69 quality %), 20 gram carclazytes and an amount of metal oxide or its precursor mix, the concentration that adds 4 milliliters is the nitric acid of 65 quality % and 30 milliliters mixed the pinching of water, it with the aperture 2 millimeters orifice plate extrusion, extrudate was left standstill 4 hours at 20 ℃, 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours make chloride absorbent.Metal oxide that each example adds and dosage, adsorbent are formed and are penetrated chlorosity and see Table 1.
Example 4～7
Following case expedition carclazyte and content are to the influence of performance of the adsorbent.
After the carclazytes (the Su Zhou industrial park limited worker of efforts of everyone bentonite department product) of getting 50 gram boehmites, 20 gram ZnO, 1 gram manganese oxide and different amounts mix, by the method for example 1 mixedly pinch, extrusion, make adsorbent after drying, the roasting.Each example carclazyte dosage, adsorbent are formed and are penetrated chlorosity and see Table 2.
As shown in Table 2, add carclazyte in the adsorbent, can suitably improve it and penetrate chlorosity.
Example 8～11
Following case expedition bentonite and content are to the influence of performance of the adsorbent.
After the bentonites (the Su Zhou industrial park limited worker of efforts of everyone bentonite department product) of getting 50 gram boehmites, 20 gram ZnO, 1 gram manganese oxide and different amounts mix, by the method for example 1 mixedly pinch, extrusion, make adsorbent after drying, the roasting.Each example bentonite dosage, adsorbent are formed and are penetrated chlorosity and see Table 3.
As shown in Table 3, add bentonite in the adsorbent, can suitably improve it and penetrate chlorosity.
Example 12～15
Following case expedition zinc oxide and content are to the influence of performance of the adsorbent.
After the zinc oxide (sky, Hunan becomes chemical company to produce) of getting 50 gram boehmites, 10 gram carclazytes, 1 gram manganese oxide and different amounts mix, mix by the method for example 1 pinch, extrusion, make adsorbent after dry, the roasting.Each example zinc oxide dosage, adsorbent are formed and are penetrated chlorosity and see Table 4.
As shown in Table 4, add zinc oxide in the adsorbent, can effectively improve it and penetrate chlorosity.
Example 16～19
Following case expedition manganese oxide and content are to the influence of performance of the adsorbent.
After the manganese oxide of getting 50 gram boehmites, 30 gram ZnO, 10 gram carclazytes and different amounts mix, by the method for example 1 mixedly pinch, extrusion, make adsorbent after drying, the roasting.Each example manganese oxide dosage, adsorbent are formed and are penetrated chlorosity and see Table 5.
As shown in Table 5, add manganese oxide in the adsorbent in right amount, can improve the chlorosity that penetrates of adsorbent.
Table 1
| Instance number | Metal oxide or its precursor dosage, gram | Adsorbent is formed, quality % | Penetrate chlorosity, quality % | ||
| Aluminium oxide | Carclazyte | Metal oxide | |||
| 1 | ZnO 40 | 31.5 | 22.8 | ZnO 45.7 | 34.8 |
| 2 | MgO 40 | 31.5 | 22.8 | MgO 45.7 | 15.7 |
| 3 | Anhydrous sodium acetate 12 | 53.0 | 38.5 | NaO 8.5 | 11.0 |
Table 2
| Instance number | The carclazyte dosage, gram | Adsorbent is formed, quality % | Penetrate chlorosity, quality % | |||
| Aluminium oxide | Carclazyte | Zinc oxide | Manganese oxide | |||
| 4 | 10 | 52.7 | 15.3 | 30.5 | 1.5 | 22.4 |
| 5 | 20 | 45.7 | 26.5 | 26.5 | 1.3 | 27.2 |
| 6 | 30 | 40.4 | 35.1 | 23.4 | 1.1 | 31.3 |
| 7 | - | 62.2 | / | 36.0 | 1.8 | 18.5 |
Table 3
| Instance number | The bentonite dosage, gram | Adsorbent is formed, quality % | Penetrate chlorosity, quality % | |||
| Aluminium oxide | Bentonite | Zinc oxide | Manganese oxide | |||
| 8 | 1 | 61.1 | 1.8 | 35.3 | 1.8 | 20.5 |
| 9 | 3 | 59.0 | 5.1 | 34.2 | 1.7 | 22.7 |
| 10 | 5 | 57.0 | 8.3 | 33.1 | 1.6 | 25.1 |
| 11 | - | 62.2 | / | 36.0 | 1.8 | 18.5 |
Table 4
| Instance number | The zinc oxide dosage, gram | Adsorbent is formed, quality % | Penetrate chlorosity, quality % | |||
| Aluminium oxide | Carclazyte | Zinc oxide | Manganese oxide | |||
| 12 | 10 | 62.2 | 18.0 | 18.0 | 1.8 | 15.4 |
| 13 | 25 | 48.9 | 14.2 | 35.5 | 1.4 | 23.6 |
| 14 | 40 | 40.4 | 11.7 | 46.8 | 1.1 | 33.3 |
| 15 | - | 71.8 | 22.0 | / | 2.2 | 11.7 |
Table 5
| Instance number | The manganese oxide dosage, gram | Adsorbent is formed, quality % | Penetrate chlorosity, quality % | |||
| Aluminium oxide | Carclazyte | Zinc oxide | Manganese oxide | |||
| 16 | 0.5 | 46.0 | 13.3 | 40 | 0.7 | 27.0 |
| 17 | 1 | 45.7 | 13.2 | 39.7 | 1.4 | 29.0 |
| 18 | 2 | 45.1 | 13.1 | 39.2 | 2.6 | 34.1 |
| 19 | - | 46.3 | 13.4 | 40.3 | / | 24.8 |
Claims (6)
1, a kind of chloride absorbent comprises the aluminium oxide of 25～80 quality %, the filler of 1～60 quality % and the metal oxide of 5～65 quality %, and described filler is selected from carclazyte or bentonite, and metal oxide is selected from zinc oxide, magnesia or sodium oxide molybdena.
2, require 1 described adsorbent according to profit, when it is characterized in that filler is selected from carclazyte in the adsorbent, its content is 10～40 quality %.
3, require 1 described adsorbent according to profit, when it is characterized in that filler is selected from bentonite in the adsorbent, its content is 1～15 quality %.
4, require 1 described adsorbent according to profit, it is characterized in that also containing in the described adsorbent manganese oxide of 0.3～5.0 quality %.
5, require 4 described adsorbents according to profit, the content that it is characterized in that described manganese oxide is 0.5～3.0 quality %.
6, require 1 described adsorbent according to profit, it is characterized in that described aluminium oxide is a gama-alumina.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100464837C (en) * | 2006-07-14 | 2009-03-04 | 华东理工大学 | Chloride absorbent |
| US9440218B2 (en) * | 2013-06-13 | 2016-09-13 | Clariant Corporation | Methods and active materials for reducing halide concentration in gas streams |
| CN104689782A (en) * | 2013-12-05 | 2015-06-10 | 无锡钻石地毯制造有限公司 | Ecological carpet hydrogen chloride adsorbent |
| CN103706324B (en) * | 2014-01-24 | 2015-09-09 | 上海方纶新材料科技有限公司 | The preparation method of modified aluminas dehydrating agent |
| CN107175067A (en) * | 2017-06-09 | 2017-09-19 | 信阳师范学院 | MnO2NaCl/ bentone adsorbents and preparation method and application |
| CN109704992A (en) * | 2018-12-18 | 2019-05-03 | 甘肃银光聚银化工有限公司 | A method of reducing toluene di-isocyanate(TDI) acidity |
| CN111603902A (en) * | 2020-05-18 | 2020-09-01 | 武汉理工大学 | Magnesium chloride-based adsorbent and preparation method thereof |
| CN111621321B (en) * | 2020-06-03 | 2023-05-19 | 中国海洋石油集团有限公司 | Porous foam liquid-phase dechlorinating agent, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079415A (en) * | 1992-06-02 | 1993-12-15 | 中国石油化工总公司石油化工科学研究院 | A kind of chloride absorbent and preparation method thereof |
| CN1114238A (en) * | 1994-06-22 | 1996-01-03 | 中国石油化工总公司化工科学研究院 | Hydrogen chloride adsorbent and preparing process thereof |
| JPH11276883A (en) * | 1998-03-27 | 1999-10-12 | Meidensha Corp | Adsorbent for hydrogen chloride and its preparation and regeneration and elimination of hydrogen chloride |
| US6558641B1 (en) * | 1998-02-06 | 2003-05-06 | Imperial Chemical Industries Plc | Absorbents |
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- 2004-12-28 CN CNB2004101028068A patent/CN100344363C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079415A (en) * | 1992-06-02 | 1993-12-15 | 中国石油化工总公司石油化工科学研究院 | A kind of chloride absorbent and preparation method thereof |
| CN1114238A (en) * | 1994-06-22 | 1996-01-03 | 中国石油化工总公司化工科学研究院 | Hydrogen chloride adsorbent and preparing process thereof |
| US6558641B1 (en) * | 1998-02-06 | 2003-05-06 | Imperial Chemical Industries Plc | Absorbents |
| JPH11276883A (en) * | 1998-03-27 | 1999-10-12 | Meidensha Corp | Adsorbent for hydrogen chloride and its preparation and regeneration and elimination of hydrogen chloride |
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