A kind of preparation method of liquid hydrocarbon hydrogen sulfide remover and renovation process thereof
Relate to the field
The present invention relates to a kind of preparation method of hydrogen sulfide remover and go up method again, this removes agent can remove hydrogen sulfide in the unsaturated liquid hydrocarbon, and avoids the unsaturated hydrocarbons polymerization.
Background technology
In the liquid hydrocarbons such as liquefied gas, the petroleum naphtha that contains unsaturated hydrocarbons, gasoline, often contain a certain amount of hydrogen sulfide, hydrogen sulfide not only has toxicity, and also can produce corrosion to equipment, therefore it need be removed.As the removal methods of hydrogen sulfide in the liquid state, have several, as utilizing sodium hydroxide solution in the gasoline pre-refining technology with the hydrogen sulfide stripping in the gasoline (Hou Xianglin chief editor, Chinese oil Refining Technologies, 82 pages, Sinopec press).This method operation is fairly simple, but this method is produced main pollution big (produce the catalytic cracking unit of 600,000 tons of FCC gasoline per year, the amount of the waste lye that pre-refining produced is about 1000 tons/a).
With cupric oxide or zinc oxide as main depriving hydrogen sulphide component, with the metal oxide with copper sulfate, cupric nitrate, venus crystals is to be total to the depriving hydrogen sulphide component, the oxygen of preparation removes agent than copper system and Zinc oxide can be used for removing of liquid hydrocarbon hydrogen sulfide, announced with the cupric oxide to be the activated adsorption component as US4224191, with the aluminum oxide is the agent that removes of preparing carriers, and this removes agent and the hydrogen sulfide in the liquid hydrocarbon can be removed fully about 82 ℃.US5177050 has announced with zinc oxide to be the adsorption activity component, is the hydrogen sulfide remover of carrier with the phosphide of aluminium, the hydrogen sulfide in the liquid hydrocarbon can be removed fully under being higher than 150 ℃ temperature.Because Zinc oxide and cupric oxide system remove the agent use temperature than higher, if contain active unsaturated component in the hydrocarbon, polymerization can take place at high temperature unsaturated component.
In addition, WO9524962 has announced a kind of hydrogen sulfide stripping method of hydrocarbon, this method be with the ventilation breather composite particles as hydrogen sulfide remover, the hydrogen sulfide in can the liquid towards degree removes; It is lower that this removes the agent use temperature, relatively good to the removal effect of hydrogen sulfide, but the ventilation breather that this method adopted is a powdery, is difficult in the industrial operation realize.
Summary of the invention
The object of the present invention is to provide a kind of use temperature low, can not cause the preparation method and the renovation process of active unsaturated hydrocarbons polymeric hydrogen sulfide remover.
The agent that removes involved in the present invention is to be carrier with the activated carbon, hydrogen sulfide remover by precipitator method preparations (Precipitation), this removes agent and the hydrogen sulfide in the liquid hydrocarbon can be removed fully at normal temperatures, can not cause the polymerization of active unsaturated component in the liquid hydrocarbon.
Above-mentioned hydrogen sulfide remover prepares as follows:
Get and a certain amount ofly have the gac of certain particle size in metal salt solution.The volume ratio of gac and metal salt solution was less than 1: 2, metal salt solution can be the soluble copper salts solution, copper sulfate such as soluble Zn salts solution, cupric nitrate, venus crystals soluble metal salts solution or its mixing solutions, stir under the room temperature and leach metal salt solution (stirring can be adopted any whipping appts) after 2~3 hours, add excessive 5%~100% the alkali lye that draws, alkali lye can be sodium carbonate solution, sodium hydrogen carbonate solution, solution of potassium carbonate, a kind of or its mixing solutions in the potassium bicarbonate solution, restir 2~3 hours, filter, be washed with distilled water to filtrate and be neutral, drying is 2~6 hours about 100 ℃.
Dried product is repeated to do twice as stated above, can obtain hydrogen sulfide remover, this removes, and the content of metal is greater than 15% in the agent, is preferably in more than 20%.
Zhi Bei hydrogen sulfide remover because the activated carbon that is adopted is the gac with high-specific surface area and flourishing pore structure, adopts the precipitator method during preparation as stated above; The metal-salt that generates distributes more even on activated carbon surface, therefore prepared as stated above hydrogen sulfide remover has reasonable hydrogen sulfide stripping performance, and this hydrogen sulfide remover can repeatedly be regenerated after adsorption of hydrogen sulfide reaches capacity, hydrogen sulfide remover after the regeneration still has certain hydrogen sulfide stripping performance, renovation process is as follows: get the hydrogen sulfide remover that adsorption of hydrogen sulfide reaches capacity and boiled in boiling water 20~30 minutes, remove liquid hydrocarbon adsorbed in the hydrogen sulfide remover, washing, filter, dry back (100~140 ℃ of drying temperatures, 4~6 hours time) load again as stated above can obtain the regenerated hydrogen sulfide remover.Hydrogen sulfide stripping method of the present invention, be to contain in the liquid hydrocarbon of hydrogen sulfide with respect to hydrogen sulfide content equivalent in the liquid hydrocarbon or excessive hydrogen sulfide remover adding, utilize any blending means, 0~80 ℃ of temperature of reaction, reaction is 2 hours under preferred 20~60 ℃ of conditions, the hydrogen sulfide in the gasoline can be removed fully.Liquid hydrocarbon feeds is the FCC catalytically cracked gasoline, and unsaturated hydrocarbons content is 40~60% in the gasoline, and liquid hydrocarbon feeds also can be liquefied gas, contains petroleum naphtha of a large amount of unsaturated hydrocarbons or the like.
Concrete enforcement
Embodiment 1
The copper-bath of getting 30 ml concns and be 1.2mol/L is in 50 milliliters Erlenmeyer flask, add the 10g granularity at 6~16 purpose apricot shell gacs, vibration absorption 4 hours, filter, get the gac that leaches in the 50ml Erlenmeyer flask, add the isocyatic sodium carbonate solution of 30ml, vibrated 4 hours, filter, be neutral with a large amount of distilled water washs to filtrate, then when 6 of 100 ℃ of dryings, to twice of the load again again of dried activated carbon, can obtain the copper salt kind hydrogen sulfide remover, this removes the CUCO that consists of of agent
3Cu (OH)
2, the content that removes metal in the agent is 23%.
Embodiment 2
Get 5g by the prepared hydrogen sulfide remover of the method for implementing 1 in the 1000ml Erlenmeyer flask, adding the 1000ml hydrogen sulfide content is the FCC gasoline (unsaturated hydrocarbons content is 40~60% in the gasoline) of 150ppm, reaction is after 2 hours down for 20 ℃ of agitation conditions, and detection exists less than hydrogen sulfide in the gasoline.
Embodiment 3
Get 5g by the prepared hydrogen sulfide remover of the method for embodiment 1 in the 1000ml Erlenmeyer flask, adding the 1000ml hydrogen sulfide content is the FCC gasoline (unsaturated hydrocarbons content is 40~60% in the gasoline) of 150ppm, reaction is after 2 hours down for 40 ℃ of agitation conditions, and detection exists less than hydrogen sulfide in the gasoline.
Embodiment 4
Get 5g by the prepared hydrogen sulfide remover of the method for implementing 1 in the 1000ml Erlenmeyer flask, adding the 1000ml hydrogen sulfide content is the FCC gasoline (unsaturated hydrocarbons content is 40~60% in the gasoline) of 150ppm, reaction is after 2 hours down for 60 ℃ of agitation conditions, and detection exists less than hydrogen sulfide in the gasoline.
Embodiment 5
Get 5g by the prepared hydrogen sulfide remover of the method for embodiment 1 in the 1000ml Erlenmeyer flask, adding the 1000ml hydrogen sulfide content is the FCC gasoline (unsaturated hydrocarbons content is 40~60% in the gasoline) of 150ppm, 40 ℃ were fully reacted 2 hours down, the gasoline that repeats to add oil-containing hydrogen sulfide after the filtration reacts, when treating that the sulfur in gasoline hydrogen concentration does not change, it is saturated to think that hydrogen sulfide remover reaches absorption.
The hydrogen sulfide remover that adsorption of hydrogen sulfide reaches capacity is regenerated; Renovation process is as follows: put the hydrogen sulfide remover of absorption after reaching capacity in the beaker of 100ml, add 80ml distilled water, boil 20min, in 120 ℃ of dry 4h down, the method for pressing embodiment 1 then load again gets final product behind the filtration washing.
Hydrogen sulfide remover after the regeneration is carried out saturated adsorption test by described method, the postcure hydrogen that obtains regenerating takes off the saturated sulfur capacity of herding except that agent, using the same method to obtain regenerating 2 times, 3 times, 4 times the saturated sulfur capacity of hydrogen sulfide remover, and the result is as table.
Regeneration times | Saturated sulfur capacity g sulphur/g hydrogen sulfide remover |
0 | 0.115 |
1 | 0.047 |
2 | 0.041 |
3 | 0.029 |
4 | 0.020 |
Accumulative total | 0.252 |
Embodiment 6
Get 5g by the hydrogen sulfide remover of the method for embodiment 5 regeneration 1 time in the Erlenmeyer flask of 1000ml, adding the 1000ml hydrogen sulfide content is the gasoline (unsaturated hydrocarbons content is 40~60% in the gasoline) of 150ppm, 40 ℃ reaction is after 2 hours down, and detection is less than the existence of hydrogen sulfide in the gasoline.
Embodiment 7
Get 5g by the hydrogen sulfide remover of the method for embodiment 5 regeneration 2 times in the Erlenmeyer flask of 1000ml, adding the 1000ml hydrogen sulfide content is the gasoline (unsaturated hydrocarbons content is 40~60% in the gasoline) of 150ppm, 40 ℃ reaction is after 2 hours down, and detection is less than the existence of hydrogen sulfide in the gasoline.
Embodiment 8
Get 5g by the hydrogen sulfide remover of the method for embodiment 5 regeneration 3 times in the Erlenmeyer flask of 1000ml, adding the 1000ml hydrogen sulfide content is the gasoline (unsaturated hydrocarbons content is 40~60% in the gasoline) of 150ppm, 40 ℃ reaction is after 2 hours down, and detection is less than the existence of hydrogen sulfide in the gasoline.
Embodiment 9
Get 5g by the hydrogen sulfide remover of the method for embodiment 5 regeneration 4 times in the Erlenmeyer flask of 1000ml, adding the 1000ml hydrogen sulfide content is the gasoline (unsaturated hydrocarbons content is 40~60% in the gasoline) of 150ppm, 40 ℃ reaction is after 2 hours down, and detection is less than the existence of hydrogen sulfide in the gasoline.