CN100482319C

CN100482319C - One-step purifying process for ammonia and methanol

Info

Publication number: CN100482319C
Application number: CNB2007100783548A
Authority: CN
Inventors: 李志义; 李晓澎
Original assignee: Individual
Current assignee: Individual
Priority date: 2007-03-30
Filing date: 2007-03-30
Publication date: 2009-04-29
Anticipated expiration: 2027-03-30
Also published as: CN101020129A

Abstract

The one-step ammonia or methanol product purifying process includes adopting purifying agent comprising SiO2, MnO2, Fe2O3, Ai2O3, ZnO and other components; passing ammonia or methanol product upwards through the purifying tank with the purifying agent for normal pressure and normal temperature adsorption, and regenerating the purifying agent through heating outside the purifying tank with air or nitrogen downward introduced. The process is simple, and can eliminate water, organic sulfide, hydrogen sulfide and other impurity effectively.

Description

Ammonia or methanol by one-step method purification method

Technical field

The invention belongs to ammonia or methanol purification technical field, be specifically related to a kind of purification method that purifies materials such as water, organic sulfur, hydrogen sulfide, sulfur dioxide in ammonia or the methyl alcohol.

Background technology

At chemical industry, a large amount of ammonia or methyl alcohol of using are as raw material and heat treatment source of the gas in the heat treatment industry, but because ammonia and methyl alcohol much are by the natural gas manufacturing or the subsidiary product after making, because the desulfurization depth of natural gas own is limited, before entering the methyl alcohol manufacturing installation behind the selexol process, still there are many sulphur, comprise organic sulfur, hydrogen sulfide and sulfur dioxide, also contain a large amount of water etc. in addition, this can have a negative impact for chemical industry and Equipment for Heating Processing, when therefore needing higher ammonia of purity or methyl alcohol in use, need elder generation to ammonia or the processing of earning of methyl alcohol, remove water, organic sulfur, hydrogen sulfide, materials such as sulfur dioxide.

BP GB2252308 discloses a kind of method that removes sour gas from gaseous mixture, this method mainly comprises with solvent and absorbs sour gas and with the vaporizing extract process spent solvent of regenerating, used solvent is made up of the aqueous mixture of dimethylethanolamine, and the concentration of dimethyl ethanol is 30%-70% (weight).Though this method can remove sour gas preferably, still exist organic sulfur and water content is big, the running cost height, there are shortcomings such as environmental pollution in complicated operation.

The method that also has a variety of purification ammonias, methyl alcohol at present, but all be to adopt multistep or at least two steps to remove materials such as wherein water, organic sulfur, hydrogen sulfide, sulfur dioxide.

Method as impurity such as H2S in the purification ammonia at present commonly used is the concentrated ammonia liquor washing, generates hydrogen sulfide ammonia, sulfuration ammonia etc. by impurity such as the H2S in the ammonia and concentrated ammonia liquor reaction, thereby impurity such as H2S removed, and reaching the order ground that purifies ammonia.The subject matter that this method exists has: 1, the H2S remaining quantity is higher in the ammonia, about 100 μ g/g; 2, organic sulfur fails to remove; 3, have secondary pollution, it is pending to produce alkaline residue; 4, the liquefied ammonia consumption is big; 5, flow process is complicated, and equipment is many.

The method of the disclosed a kind of purifying and recovering ammonia gas of for example domestic patent CN1393405A again, this method is that to utilize active carbon or aluminium oxide to adopt two-step method to purify be the method for crystallization-absorption, earlier ammonia is entered crystallizing tank, inject simultaneously liquefied ammonia in proportion and form low temperature, the condition of low temperature the hydrogen sulfide and the reactant of ammonia are sublimated into crystallization attached to the crystallizing tank that crystallization plates is housed in, residual then hydrogen sulfide and ammonia enter in the adsorption tanks that adsorbent is housed.This method can remove hydrogen sulfide preferably, but crystallizing tank and adsorption tanks all have the temperature and pressure requirement, and has the regeneration technology complexity, and it is insufficient to regenerate, disadvantages such as adsorbent weak point in service life.

Summary of the invention

Be deficiency at the prior art existence order of the present invention, a kind of ammonia or methanol purification method are provided, adopt normal pressure, normal temperature absorption, one step realized purifying, electrical heating blowing air or nitrogen regeneration, and method is simple, can efficiently remove the impurity such as water, organic sulfur, hydrogen sulfide and sulfur dioxide in ammonia or the methyl alcohol, and the cleanser use of can repeatedly regenerating, the equipment less investment, expense is low.

The purification method that the present invention proposes is as follows:

1, a step purifies: ammonia to be clean or methanol gas are fed by the purification pot bottom that cleanser is housed, and gas pressure after cleanser normal temperature, normal pressure absorption, is exported by purification pot top in purification pot below 0.1Mpa.This earning agent is with SiO ₂Be Main Ingredients and Appearance, other is added with MnO ₂, Fe ₂O ₃, Ai ₂O ₃, the ZnO composition, the porous mass that sinters into, the percentage by weight of each composition is as follows: SiO ₂50～75%, MnO ₂0.1 Fe～5%, ₂O ₃0.1 Ai～5%, ₂O ₃5～14.5%, ZnO 0.1～3%; Also can add each K of 0.1～3% in addition ₂O, CaO, Na ₂O and ZrO ₂

2, cleanser regeneration: when impurity such as the water of cleanser absorption, organic sulfur, hydrogen sulfide, sulfur dioxide reach capacity, it is regenerated:

A, stop ammonia or methanol gas and feed, purification pot is carried out external heat, temperature controlled maximum magnitude is between 100 ℃～600 ℃, and temperature controlled preferred range is between 150 ℃-550 ℃.

B, under normal pressure, by purification pot top to bottom bubbling air or nitrogen regeneration, when regenerating behind the certain hour by instrument detecting regeneration emission gases, when impurity contents such as water, organic sulfur, hydrogen sulfide, sulfur dioxide all do not have in the regeneration emission gases, the adsorbate that is cleanser is by full scale clearance, and regeneration finishes.

The purification method of this method has merged chemistry, electrochemical action, department of physics's suction-operated and filtration, relevant reaction equation for example:

H2S+Fe2O3→FeS+H2O

Advantage of the present invention is as follows:

1, this method is owing to adopted special cleanser, impurity such as the water that it can remove in ammonia or the methyl alcohol to be contained simultaneously, organic sulfur, hydrogen sulfide, sulfur dioxide, thereby purification work one step is finished, and cleaning equipment is simple to operate, occupations of land is little, less investment, the low suitable commercial Application of expense.

2, heating blowing air or nitrogen regeneration under the normal pressure have been adopted in the regeneration of cleanser, regeneration is effectively simple, the cleanser long service life.

3, the purifying regeneration process has been adopted the design of reverse gas circuit, ammonia or methyl alcohol are fed downwards by purification pot top when promptly purifying, and air is upwards fed by the purification pot bottom during regeneration, and this is all very favourable to purifying with regeneration.

4, purification efficiency height, decontamination index can reach: organic sulfur＜3mg/m3, hydrogen sulfide＜1mg/m3, sulfur dioxide＜1mg/m3, moisture content dew point＜-42 ℃ (the trace water detector detects conversion).

The inventive method can be widely used in industries such as chemical industry, heat treatment.

Description of drawings

Fig. 1 is the structural representation of the purification pot of this method use.

The specific embodiment

The invention will be further described below in conjunction with embodiment and accompanying drawing:

Referring to Fig. 1, in ammonia to be clean or methyl alcohol fed jar by purification pot 1 bottom of built-in purifying agent 2, in purification pot 1 after the absorption of cleanser 2 normal temperature, normal pressure, impurity such as the water in ammonia or the methanol gas, organic sulfur, hydrogen sulfide, sulfur dioxide are by cleanser 2 absorption, ammonia after the purification or methanol gas are finished purification by the output of purification pot 1 top.When impurity such as earning agent 2 adsorbed water, organic sulfur, hydrogen sulfide, sulfur dioxide etc. reach capacity, need it is regenerated, the step of regeneration is: the first step, stop ammonia or methanol gas earlier and feed, by from purification pot 1 top bubbling air or nitrogen, after the ammonia in the jar or methyl alcohol are discharged in wait, carry out external heat with 3 pairs of purification pots of heating 1 again, make it temperature and reach between 100 ℃～600 ℃ of the range of set temperature, preferably be controlled between 150 ℃-550 ℃.Second goes on foot, continues simultaneously to feed regeneration air or nitrogen downwards by earning jar 1 top, regeneration air or nitrogen carry impurity such as water in the cleanser, organic sulfur, hydrogen sulfide, sulfur dioxide and are exported by purification pot 1 bottom, when regenerating behind certain hour, by instrument detecting regeneration emission gases, when impurity contents such as water, organic sulfur, hydrogen sulfide, sulfur dioxide all do not have in the regeneration emission gases, the adsorbate that is cleanser is by full scale clearance, and regeneration finishes.

Employed cleanser component content proportioning following (weight %):

	SiO ₂	Ai ₂O ₃	MnO ₂	Fe ₂O ₃	K ₂O	CaO	Na ₂O	ZrO ₂	ZnO
	SiO ₂	Ai ₂O ₃	MnO ₂	Fe ₂O ₃	K ₂O	CaO	Na ₂O	ZrO ₂	ZnO	Example 1	73％	14％	5％	5％	0％	0％	0％	0％	3％
Example 2	71％	14.5％	3％	2.5％	3％	0％	0％	3％	3％	Example 1	73％	14％	5％	5％	0％	0％	0％	0％	3％

Example 3	66.4％	14.5％	5％	5％	0％	1％	0％	2％	0.1％
Example 3	66.4％	14.5％	5％	5％	0％	1％	0％	2％	0.1％	Example 4	65％	14.5％	4％	5％	3％	3％	3％	2％	0.5％
Example 5	61.5％	14.5％	5％	4％	3％	3％	3％	3％	3％	Example 4	65％	14.5％	4％	5％	3％	3％	3％	2％	0.5％
Example 5	61.5％	14.5％	5％	4％	3％	3％	3％	3％	3％	Example 6	65％	10％	5％	5％	3％	3％	3％	3％	3％
Example 7	65％	14.5％	5％	5％	3％	3％	3％	1.4％	0.1％	Example 6	65％	10％	5％	5％	3％	3％	3％	3％	3％
Example 7	65％	14.5％	5％	5％	3％	3％	3％	1.4％	0.1％	Example 8	65％	14.5％	4％	5％	3％	3％	2％	2％	1.5％
Example 9	63％	14％	5％	5％	3％	3％	3％	3％	1％	Example 8	65％	14.5％	4％	5％	3％	3％	2％	2％	1.5％

Above-mentioned raw materials through sintering cellular into, is put into purification pot and used.

Through adopting this method that ammonia or the methanol feedstock that generalization factory uses purified, it is as follows to purify back effect contrast:

Claims

1, a kind of ammonia or methanol purification method, step is as follows:

(1) one step purified: ammonia to be clean or methanol gas are fed by the purification pot bottom that cleanser is housed, and gas pressure after cleanser normal temperature, normal pressure absorption, is exported by purification pot top in purification pot below 0.1Mpa; This cleanser is a porous mass, and described porous mass is by SiO ₂, MnO ₂, Fe ₂O ₃, Ai ₂O ₃, ZnO sinters into, the percentage by weight of each composition is as follows in the described porous mass: SiO ₂50～75%, MnO ₂0.1 Fe～5%, ₂O ₃0.1 Ai～5%, ₂O ₃5～14.5%, ZnO 0.1～3%;

(2) regeneration: when the moisture content of cleanser absorption, when sulfur-containing impurities reaches capacity, it is regenerated:

A, stop ammonia or methanol gas and feed, purification pot is carried out external heat, temperature is controlled between 100 ℃～600 ℃;

B, under normal pressure, to bottom bubbling air or nitrogen regeneration, by instrument detecting regeneration emission gases, when moisture content and sulfur-containing impurities did not all have in the regeneration emission gases, promptly the adsorbate of cleanser was by full scale clearance by purification pot top, regeneration finishes.

2, ammonia according to claim 1 or methanol purification method is characterized in that: described cleanser also includes each K of 0.1～3% of percentage by weight ₂O, CaO, Na ₂O and ZrO ₂

3, ammonia according to claim 1 or methanol purification method is characterized in that: during cleanser regeneration, temperature controlled preferred range is between 150 ℃-550 ℃.