CN1037942C - Hydrogen chloride adsorbing agent and preparation method thereof - Google Patents
Hydrogen chloride adsorbing agent and preparation method thereof Download PDFInfo
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- CN1037942C CN1037942C CN 92103886 CN92103886A CN1037942C CN 1037942 C CN1037942 C CN 1037942C CN 92103886 CN92103886 CN 92103886 CN 92103886 A CN92103886 A CN 92103886A CN 1037942 C CN1037942 C CN 1037942C
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- hydrogen chloride
- adsorbent
- earth metal
- carbonate
- alumina
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Abstract
The present invention relates to a chemosorbent for removing hydrogen chloride impurities from gas or liquid hydrocarbon, which is composed of gamma-alumina and an auxiliary agent of alkali carbonate or alkaline earth metal carbonate. The preparation method can adopt any kind of a strip mixing squeezing method or an immersion method or a ball rolling method or a sheet pressing molding method. The chemosorbent has strong capability for removing hydrogen chloride and reduces the content of hydrogen chloride impurities from gas or liquid hydrocarbon into below 0.5 ppm. At this time, the adsorption quantity of the hydrogen chloride on the chemosorbent can achieve 25% (weight).
Description
The present invention relates to a kind of chemosorbent and preparation method thereof, this adsorbent can remove the hydrogen chloride impurity that it contains from gas or liquid hydrocarbon.
In petrochemical industry was produced, many technical process can both produce the hydrogen chloride impurity of trace, thereby normal production operation is adversely affected.For example, in the catalytic reforming process of oil plant, the chlorine constituent element that contains on the reforming catalyst can constantly run off, and keeps certain acidity for making catalyst, needs constantly to inject organic chloride in running operation.The chlorine constituent element that runs off in reforming process and the chloride of injection all are contained in reformer hydrogen and reformed oil with the form of hydrogen chloride.These hydrogen chloride impurities can pollution systems, etching apparatus, but also generate the chlorination ammonium salt of solid and blocking pipeline with the ammonia effect in can the upstream device in process units.In addition, other might cause shut-down problem unnecessary in the production can also to cause some.Therefore, in order to keep normal operation operation, must adopt suitable method to remove hydrogen chloride impurity in gas and the liquid hydrocarbon.
The method that removes hydrogen chloride commonly used at present is alkali cleaning and absorption, opens clear 58-58135 as the spy and removes hydrogen chloride with alkali cleaning at normal temperatures.Because the acid-base neutralization reaction speed is fast, it is fine that this method removes the hydrogen chloride effect.But alkali wash needs a series of equipment, except that caustic wash tower, auxiliary equipment such as alkali lye storage tank, circulating pump, liquid circulating pipe line, control instrument and analytical instrument will be arranged also.Also cumbersome in operation, in addition, alkali wash also can make and contain too much moisture content in the gas.
Using adsorbent to remove hydrogen chloride also has many reports, and as US3,935,259 use the chloride absorbent that contains zinc oxide and alkaline calcium compound, and this adsorbent need use under higher temperature, therefore heat power supply device must be arranged, and has increased energy consumption.
US4,374,654 use activated alumina and adsorbent of molecular sieve to remove hydrogen chloride.The activated alumina price is lower, but the adsorption capacity of hydrogen chloride is also low.Though the adsorption capacity of molecular sieve is higher than activated alumina, price is also much higher, and in addition, it is a lot of that the hydrogen chloride that has been adsorbed also can make the intensity of molecular sieve descend.
The adsorbent that alkali metal compound or alkaline earth metal compound are loaded on the carrier also has some reports.Chloride absorbent as SU1255175 is by Na
2SO
3, Na
2S
2O
3, K
2SO
3Or K
2S
2O
3Be immersed on the wood chip and make.The spy opens the chloride absorbent of clear 79-35188 by Na
2CO
3Be loaded in active carbon, porous TiO
2Deng making on the inert substance.
US4, the chloride absorbent of 639,259 reports is loaded on the aluminium oxide by the alkaline earth metal compound auxiliary agent to be made, and used aluminium oxide is the transition state of alumina with χ-ρ-η phase structure, and the content of alkaline-earth metal is 0.5～45% (weight).According to the data of this patent disclosure, this adsorbent can be reduced to hydrogen chloride in gas content below the 1ppm.Penetrate that the adsorbance of hydrogen chloride is 9.6～20.3% (weight) when adsorbent bed.
By the performance of several chloride absorbents of above prior art as can be seen, effect is preferably as US4,639,259 adsorbent, contain two components of activated alumina and metallic compound auxiliary agent, activated alumina also has function vector concurrently except that absorption property is arranged, make the metallic compound can load on it; And metallic compound itself is an alkaline matter, in the decapacitation and outside the acidity of hydrogen chloride, improves the promoter effect of activated alumina adsorption capacity in addition.
Purpose of the present invention, just provide a kind of raw material be easy to get, inexpensive, and to the absorption property of hydrogen chloride than the better adsorbent of prior art.
Adsorbent feature of the present invention is to be adsorbent with the gama-alumina, is auxiliary agent with alkali carbonate or alkaline earth metal carbonate.Tenor accounts for 1～16% (weight) of adsorbent of the present invention.
Alkali metal in the adsorbent of the present invention or alkaline earth metal carbonate, can be directly with carbonate as the preparation raw material, also can be indirectly with the compound (as acetate, bicarbonate etc.) that can be decomposed into carbonate after being heated as preparing raw material.If directly with carbonate during as raw material, this carbonate must be water miscible, as sodium carbonate, potash.And magnesium carbonate, calcium carbonate, brium carbonate are because of water insoluble, so can not be directly as raw material.If during as raw material, this compound also must be water miscible, as saleratus with the compound that can be decomposed into carbonate after being heated.So long as a certain alkali metal or alkaline earth metal compound energy are water-soluble and can change carbonate after being heated into, this compound just can be as the raw material of adsorbent of the present invention, also can use even the carbonate that generates after being subjected to thermal transition is water insoluble, for example magnesium acetate (it is converted into water-fast magnesium carbonate after being heated).
The gama-alumina of adsorbent of the present invention can be to be made by aluminium hydroxide or diaspore, and as boehmite, boehmite, softening aluminium stone etc., these compounds can be converted into gama-alumina through after the suitable temperature roasting.Certainly, also can directly use gama-alumina as the preparation raw material.
Preparation of adsorbent method of the present invention can adopt following a kind of:
1, mixes pinching bar method
After various raw materials are ground to form fine powder by 80 sieve meshes, driedly be mixed evenly, add the nitric acid of entry or 0.1～40% concentration or acetic acid solution and mix and pinch the back extrusion, the consumption of water or acid solution is 50～95% (weight) of solid material.For 0.1～10% (weight) the sesbania powder or the oxalic acid that make extrusion can add solid material are smoothly made extrusion aid.Elder generation with drying materials, was finished product in 0.5～10 hour 200～800 ℃ of following roastings again after the extrusion under 30～140 ℃.
2, roller forming method
After various raw materials are ground to form fine powder by 80 sieve meshes, driedly be mixed evenly, in 0.1～20% concentration of aqueous solution limit spin of nodulizer inner edge water spray or nitric acid, acetate, the consumption of water or acid solution is 50～95% (weight) of solid material.For improving the intensity of spherolite, can add the binding agent of 0.1～20% (weight), for example alchlor.After the spin earlier 30～140 ℃ with drying materials, be finished product 200～800 ℃ of roastings after 0.5～10 hour again.
3, infusion process
First preparation gama-alumina, or be raw material with the gama-alumina directly is with carbonate or can be converted into the compound water solution dipping of carbonate after being heated.Flood after 0.1～24 hour, earlier 30～140 ℃ with drying materials 1～10 hour, be finished product 200～800 ℃ of following roastings after 0.5～10 hour again.
4, additive method
As long as above-mentioned raw material can be combined, and made it certain intensity, this method just can be used.For example, can adopt the compression molding method, also can use and mix pinching bar method or rolling ball method, and then use infusion process.
Should be noted that, no matter adopt any method, if the raw material that uses is the compound that can be converted into carbonate after being heated, moulding and the oven dry after semi-finished product roasting in the end the time, its temperature should be able to guarantee that this compound changes into carbonate really, but the decomposition temperature that can not be higher than carbonate can not be destroyed the phase structure of gama-alumina.
Adsorbent of the present invention both can be used for gas removal hydrogen chloride, also can be used for the hydrogen chloride that removes of liquid hydrocarbon.When using adsorbent of the present invention, the hydrogen chloride impurity content in gas and the liquid hydrocarbon can be reduced to below the 0.5ppm.At this moment, it penetrates (break-through) hydrogen chloride adsorbance and can reach 25% (weight).
Below further adsorbent of the present invention and absorption property thereof are given a detailed account with embodiment.
Embodiment 1
Present embodiment is to be raw material with calcium acetate and boehmite, is equipped with adsorbent of the present invention and measures its hydrogen chloride absorption property with the kneading and compacting legal system.
(Shandong Aluminum Plant produces 4 parts of each 25 gram boehmites, 850 ℃ of roastings 1 hour, burning residual 68.5%) (is produced from the Beijing Chemical Plant different amount one water calcium acetates with 4 parts that enumerate in table 1, analyze pure) be placed on dried even, the porphyrize of being mixed in the container, by 100 mesh sieve orders, 36% acetate (the Beijing Chemical Plant's product that adds 1.7 milliliters, analyze pure) solution and 8.5 ml waters, mix and pinch into plastic semi-solid, use the orifice plate extrusion of 2 millimeters of diameters immediately, 100 ℃ of oven dry 4 hours, promptly make chloride absorbent of the present invention after 2 hours 450 ℃ of roastings.
With above-mentioned adsorbent difference porphyrize, getting each 1.8 milliliters of 40～60 sieve mesh particles, to be respectively charged into internal diameter be in 6 millimeters the quartz glass tube, under 500 hours-1 condition of air speed, feed and contain the nitrogen that hydrogen chloride and water are 1000ppm, constantly detect hydrogen chloride content in the gas of bed outlet.When hydrogen chloride content is higher than 0.5ppm, stop ventilation.Analyze the hydrogen chloride content in the adsorbent, this amount is and penetrates (Break-through) adsorbance.Result of the test sees Table 1.US4,639,259 embodiment 3 data are also listed simultaneously in reference as a comparison in table 1.
Table 1
[notes]: (1) hydrogen chloride adsorbance with ion selective electrode method measure (" reforming process analytical method compilation ",
| Adsorbent of the present invention | Contrast is with reference to adsorbent | |||
| One water calcium acetate addition (gram) | Ca content %, (weight) | HCl penetrates adsorbance %, (weight) | Ca content %, (weight) | HCl penetrates adsorbance %, (weight) |
| 1.9 3.8 5.7 7.6 | 2.4 4.5 6.3 8.0 | 18.6 21.8 22.3 22.5 | 0.5 1.0 4.0 9.0 11.0 32.4 | 11.7 12.5 14.6 18.4 19.3 20.3 |
Research Institute of Petro-Chemical Engineering compiles)
(2) the hydride hydrogen content in gas and the liquid hydrocarbon is after absorbing with alkali lye, to use the mercuric thiocyanate colorimetric
Method is measured.
Embodiment 2
Present embodiment is to use the immersion process for preparing chloride absorbent.(Shandong Aluminum Plant produces to take by weighing 25 gram boehmites, 850 ℃ of roastings 1 hour, burn residual 68.5%), porphyrize is to passing through 160 sieve meshes, the acetic acid solution and 10 ml waters that add 2 milliliter 36% mix and pinch into plastic semi-solid, with the orifice plate extrusion of 2 millimeters of diameters, 100 ℃ of oven dry 4 hours, 450 ℃ of roastings promptly obtained the gamma-aluminium oxide carrier strip after 3 hours.
Take by weighing 3 parts of above-mentioned gama-aluminas that make of each 25 gram, fractureing becomes to be about 1 centimetre billet.Taking by weighing a water calcium acetate (Beijing Chemical Plant, analyze pure), four water magnesium acetates (permanent letter chemical plant, Shanghai is analyzed pure) and barium acetate (Beijing doube bridge pharmaceutical factory capital river reagent subsidiary factory analyzes pure) respectively as the consumption of enumerating in the table 2 respectively is dissolved in 25 ml waters.The gama-alumina billet that took by weighing is immersed respectively in the solution, flood and take out the gama-alumina billet after 2 hours.100 ℃ of oven dry 4 hours, then at 400 ℃ of roastings adsorbent that gets product after 2 hours.
Chlorination chlorine penetrates adsorbance and measures identically with embodiment 1, and measurement result sees Table 2, and with US4,639,259 embodiment 2 data are listed reference as a comparison in table 2.
Table 2
Annotate: * is by aas determination.
| Adsorbent of the present invention | Contrast is with reference to adsorbent | ||||
| The auxiliary agent that adds | The adsorbent finished product | Alkaline-earth metal and content %, (weight) | HCl penetrates adsorbance %, (weight) | ||
| The compound title | Addition in the maceration extract (gram) | Alkaline-earth metal and content * %, (weight) | HCl penetrates adsorbance %, (weight) | ||
| One water calcium acetate, four water magnesium acetate barium acetates | 2 7 8 | Ca，1.0 Mg，2.3 Ba，12.4 | 19.8 26.0 23.1 | Ca，1.2 Ca，2.8 Mg，1.0 Mg，2.5 Ba，1.3 Ba，3.2 | 13.3 14.1 13.6 13.8 9.6 10.2 |
Embodiment 3
Present embodiment is to be equipped with adsorbent with the roller forming legal system.Used raw material is boehmite and calcium acetate.
Spin dish diameter is 28 centimetres, coils dark 12 centimetres, and the angle of spin dish and vertical direction is 30 degree.
(Shandong Aluminum Plant produces to take by weighing 132 gram boehmites, 850 ℃ of roastings 1 hour, burn residual 76%, by 100 sieve meshes) and 24.5 grams, one water calcium acetate (Beijing Chemical Plant, analyze pure, by 100 sieve meshes) put into the spin dish behind the mixing, (Shunyi, Beijing Lee satisfies the chemical plant to start behind the bowling machine the rare nitric acid that under ball dish rotating speed is 40 rev/mins condition, slowly sprays into 62 ml concns 1.5% (weight), analyze pure) and keep rotation until forming bead, the diameter of bead is that 2～4 millis come.
Bead after the moulding promptly obtains the adsorbent finished product 520 ℃ of roastings then 100 ℃ of oven dry 2 hours after 2 hours.The calcium content of this adsorbent is 4.9% (weight).Record according to the test method of embodiment 1 that to penetrate the hydrogen chloride adsorbance be 17.4% (weight).
Embodiment 4
Present embodiment is with infusion process and mixes the adsorbent that pinching bar legal system is equipped with alkali metal containing carbonate.The used gamma-aluminium oxide carrier of infusion process is two kinds in the carrier of embodiment 2 and a commodity aluminium oxide (Wenzhou alumina producer produces, and the WHA-101 type is spherical, 4.8 millimeters of φ).Alkali metal promoter is sodium carbonate (Beijing Chemical Plant analyzes pure), sodium acid carbonate (Beijing Chemical Plant analyzes pure) and potash (Beijing Chemical Plant analyzes pure).Use infusion process, be dissolved in 20 ml waters after taking by weighing respectively by the auxiliary dosage in the table 3, respectively add 20 gram alumina supports again, flood and take out carrier after 2 hours, in 100 ℃ of oven dry 4 hours, 550 ℃ of roastings promptly got the adsorbent finished product after 4 hours.
Mix the thin aluminium stone of plan (Shandong Aluminum Plant's product that the pinching bar method of forming is got two parts of each 20 grams, 850 ℃ of roastings 1 hour, burn residual 68.5%), list with table 3 respectively that metallic compound auxiliary agent through weighing is dried to be mixed that even (sodium acetate trihydrate wherein is that sell in purchasing station, China Drug Co. Beijing, analyze pure), porphyrize is to passing through 100 sieve meshes, (Shunyi, Beijing Lee satisfies the chemical plant to add 8.5 milliliters 16% nitric acid, analyze pure), mix that to pinch into behind the semi-solid with diameter be 2 millimeters orifice plate extrusion, 100 ℃ of oven dry 4 hours, 650 ℃ of roastings promptly got the adsorbent finished product in 2 hours.
The hydrogen chloride of measuring above adsorbent according to method and the condition of embodiment 1 penetrates adsorbance, and the result also is listed in the table 3.
Table 3
[notes] * is by aas determination.
| The auxiliary agent title | Promoter addition (gram) | The preparation method | The gama-alumina source | Adsorbent product caustic soda tenor %, (weight) | Hydrogen chloride adsorbance %, (weight) |
| Sodium carbonate sodium acid carbonate potash potash sodium acetate trihydrate sodium acid carbonate | 4.6 1.8 6.0 6.0 6.0 3.7 | Dipping dipping dipping dipping mixes the pinching bar and mixes the pinching bar | With embodiment 1 with embodiment 1 with embodiment 1 WHA-101 boehmite boehmite | 9.0* 2.1* 12.9* 10.5* 5.8 5.8 | 19.2 16.3 15.3 1 3.3 25.2 22.2 |
Embodiment 5
Present embodiment is used for the hydrogen chloride that removes of liquid hydrocarbon for adsorbent of the present invention.Getting calcic among the embodiment 1 is adsorbent 1.05 grams of 4.5% (weight), is crushed to the particle of 20～40 sieve meshes, and the internal diameter of packing into is in 10.0 millimeters the glass tube.So that per hour 8.5 milliliters flow velocity is constantly by containing the gasoline of 10～100ppm hydrogen chloride, hydrogen chloride content surpasses 0.5ppm in effluent, and it is 12.7% (weight) that hydrogen chloride penetrates adsorbance, and time of break-through is 35 days.
Claims (7)
1. chemosorbent that removes hydrogen chloride in gas or the liquid hydrocarbon is characterized in that this adsorbent is made up of alkaline earth metal carbonate and gama-alumina, and wherein alkaline-earth metal accounts for 1～16% of adsorbent gross weight.
2. according to the described adsorbent of claim 1, it is characterized in that described alkaline-earth metal is calcium, magnesium, barium.
3. method for preparing the described adsorbent of claim 1, it is characterized in that the gama-alumina that will can change the water-soluble alkali earth metal compound mixed-forming of carbonate after gama-alumina precursor and the roasting into or directly use above-mentioned alkaline earth metal compound dip forming, drying, 400～520 ℃ of roastings 2～4 hours.
4. in accordance with the method for claim 3, it is characterized in that described water-soluble alkali earth metal compound is the alkaline-earth metal acetate.
5. in accordance with the method for claim 4, it is characterized in that described alkaline earth metal compound is calcium acetate, magnesium acetate, barium acetate.
6. in accordance with the method for claim 3, it is characterized in that described gama-alumina precursor is selected from boehmite, boehmite, softening aluminium stone.
7. in accordance with the method for claim 3, it is characterized in that described mixed-forming is extruded moulding or roller forming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92103886 CN1037942C (en) | 1992-06-02 | 1992-06-02 | Hydrogen chloride adsorbing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92103886 CN1037942C (en) | 1992-06-02 | 1992-06-02 | Hydrogen chloride adsorbing agent and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1079415A CN1079415A (en) | 1993-12-15 |
| CN1037942C true CN1037942C (en) | 1998-04-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 92103886 Expired - Lifetime CN1037942C (en) | 1992-06-02 | 1992-06-02 | Hydrogen chloride adsorbing agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101193691B (en) * | 2005-05-06 | 2017-03-15 | 环球油品公司 | For removing the scavenger of acid gas in fluid stream |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1046214C (en) * | 1994-06-22 | 1999-11-10 | 中国石油化工总公司石油化工科学研究院 | Hydrogen chloride adsorbent and preparing process thereof |
| CN100344363C (en) * | 2004-12-28 | 2007-10-24 | 中国石油化工股份有限公司 | Hydrochloric sorbent, and preparation mehtod |
| CN100453147C (en) * | 2005-12-07 | 2009-01-21 | 西北化工研究院 | Antichlor for catalytic reforming regenerated gas and preparation method |
| CN105498682B (en) * | 2015-12-07 | 2018-04-10 | 上海绿强新材料有限公司 | A kind of mesoporous chloride scavenger and preparation method thereof |
| CN107282004A (en) * | 2017-07-17 | 2017-10-24 | 中央军委后勤保障部油料研究所 | It is a kind of for solid base deacidification agent of polymethoxy dialkyl ether depickling subtractive process and preparation method thereof |
| CN110885699B (en) * | 2018-09-07 | 2021-12-24 | 中国石化扬子石油化工有限公司 | Dechlorinating agent with large pore volume and pore diameter as well as preparation method and application thereof |
| CN111408336A (en) * | 2020-03-18 | 2020-07-14 | 鲁西催化剂有限公司 | Aluminum oxide dechlorinating agent and preparation method thereof |
-
1992
- 1992-06-02 CN CN 92103886 patent/CN1037942C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101193691B (en) * | 2005-05-06 | 2017-03-15 | 环球油品公司 | For removing the scavenger of acid gas in fluid stream |
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| Publication number | Publication date |
|---|---|
| CN1079415A (en) | 1993-12-15 |
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