CN102051244B - High-efficiency purification desulfurizer for high-acid oil and gas - Google Patents

Abstract

Translated fromChinese

本发明属石油天然气净化技术领域，涉及一种从高酸性石油天然气中高效净化脱除酸性组分的脱硫剂。含有10～85%(wt)的醇胺化合物、15～75%(wt)的含氧和/或氮杂环化合物A、0.1～30%(wt)的含氧和/或氮杂环化合物B、0.1～30%(wt)的含硫杂环化合物、以及10～80%(wt)的水。采用本发明脱硫剂，能够将高酸性石油天然气中的有机硫、H₂S和CO₂分别由约1000mg/Nm³、约15%(mol)和约9%(mol)降至20mg/Nm³以下、5mg/Nm³以下和0.1%(mol)以下，有机硫脱除率最高可达98%以上。原料高酸性石油天然气的压力可在0.1MPa至8.5MPa。与普通醇胺溶剂相比，本发明脱硫剂具有脱硫率高、稳定性好、再生能耗低、跑损少、起泡少等显著优点，对于高硫含量、特别是高有机硫含量石油天然气的净化具有明显效用。

The invention belongs to the technical field of petroleum and natural gas purification, and relates to a desulfurizer for efficiently purifying and removing acidic components from highly acidic petroleum and natural gas. Containing 10-85% (wt) of alcohol amine compound, 15-75% (wt) of oxygen-containing and/or nitrogen-containing heterocyclic compound A, and 0.1-30% (wt) of oxygen-containing and/or nitrogen-containing heterocyclic compound B , 0.1-30% (wt) sulfur-containing heterocyclic compound, and 10-80% (wt) water. By using the desulfurizer of the present invention, organic sulfur, H₂ S and CO₂ in highly acidic petroleum and natural gas can be reduced from about 1000 mg/Nm³ , about 15% (mol) and about 9% (mol) to below 20 mg/Nm³ respectively , less than 5mg/Nm³ and less than 0.1% (mol), the organic sulfur removal rate can reach up to more than 98%. The pressure of raw material high-acid oil and gas can be between 0.1MPa and 8.5MPa. Compared with ordinary alcohol amine solvents, the desulfurizer of the present invention has significant advantages such as high desulfurization rate, good stability, low regeneration energy consumption, less running loss, and less foaming. It is suitable for oil and gas with high sulfur content, especially high organic sulfur content. The purification has obvious effect.

Description

The high-efficient purification sweetening agent of peracidity oil and gas

Technical field: the invention belongs to oil and gas purification techniques field, be specifically related to a kind of from peracidity oil and gas, especially from containing high concentration CO S, H₂in the acid oil and gas of S and mercaptan sulfides, efficiently remove the sweetening agent of acidic components.

Background technology: conventionally contain various acidic components from the Sweet natural gas of gas field extraction, these acidic components mainly comprise H₂s, COS and RSH sulfides and CO₂.Acidic components type and content in each gas field Sweet natural gas differ greatly, same gas field acidic components content in its Sweet natural gas of different steps of exploitation is also different, and in Sweet natural gas, organic sulfur content can have with the prolongation of gas-field exploitation time increase in various degree conventionally.

The CO of high density₂can reduce the calorific value of Sweet natural gas; H₂the existence of S not only can produce to transport pipe corrosion but also serious harm user's health; And COS is as the main component of contained organosulfur in Sweet natural gas, if it is not removed, can make on the one hand to take the downstream chemical process poisoning of catalyst that Sweet natural gas is raw material, on the other hand, COS unprocessed and that be discharged in atmosphere can form SO₂, promote photochemical reaction, bring serious environmental problem.Meanwhile, even if these sulfide also have insufferable smell under extremely low concentration level.Therefore Sweet natural gas manage defeated before, contained acidic components especially sulfide must be removed to particular value.For example GB17820-1999 stipulates H in the civilian secondary Sweet natural gas of China₂s≤20mg/Nm³, total sulfur≤200mg/Nm³, CO₂≤ 3% (mol).

Alkanolamine method is the common method that removes these acidic components, and conventional hydramine has monoethanolamine (MEA), diethanolamine (DEA), methyl monoethanolamine (MMEA), diethylethanolamine (DEEA), trolamine (TEA), diisopropanolamine (DIPA) (DIPA), diglycolamine (DGA) and N methyldiethanol amine (MDEA).Conventionally these hydramine can remove most H in Sweet natural gas₂s and CO₂, but use merely hydramine to be conventionally difficult to effective elimination organosulfur.As MEA and DEA are about respectively 45%-50%, 20-25% and 0-10% to the decreasing ratio of thiomethyl alcohol, sulfur alcohol and propylmercaptan.For the COS of effective elimination Sweet natural gas middle and high concentration, known technique often adopts syllogic flow process, and two absorption towers add a COS hydrolysis reactor, and first sour natural gas removes most H in the first absorption tower₂s and CO₂, after intensification, enter hydrolysis reactor and make COS hydrolysis, then lower the temperature and further remove CO remaining and that hydrolysis reaction generates by second absorption tower₂and H₂s.Because whole process has experienced intensification and the temperature-fall period of unstripped gas, energy consumption is increased, technical process is complicated.And this technique cannot guarantee the effective elimination to high density mercaptan compound.

If adopt a kind of absorption agent organic sulfides such as high concentration CO S and mercaptan to good removal effect, the single stage method that realizes each acidic components removes, and can simplify technique, reduces energy consumption.

Overwhelming majority workers are all by allocating appropriate secondary solvent in the solution that MDEA is main body and improve the removal effect to organosulfur to take, to further reducing the total sulfur content purifying in oil and gas.

US4808765 adopts the technique that gas is contacted with NaOH with MDEA, DIPA respectively to remove respectively the H in air-flow₂s, COS and mercaptan, Processes and apparatus complex.

US4462968 by adding H in treatment solution₂o₂reach the object that removes mercaptan, but be only applicable to concentrations of mercaptans lower than 50mg/Nm³unstripped gas.

In the patent US4336233 of BASF AG, described and take MDEA as main solvent, and the piperazine that adds 0.05～0.8mol/L is that activator removes the H in gas mixture₂s, CO₂and COS.

US6740230B1 and 6337059B1 be take equally the MDEA of piperazine activation and are removed the H in sour gas as solvent₂s, CO₂organic sulfide with lower concentration.

It is main solvent that CN1421264A and 1887406A all be take MDEA and bulky amine, and adds appropriate solubility promoter and catalyzer to remove the H in gaseous mixture₂s and most of organosulfur.

Aforesaid method does not all relate to high simultaneously high containing H containing organosulfur₂the decontamination effect improving of the oil and gas of S.H in oil and gas₂the content of S is up to 15% (mol) left and right, and organic sulfur content surpasses 600mg/Nm simultaneously³, even reach 2000mg/Nm³time, adopt above-mentioned solvent be all difficult to make to purify in oil and gas acidic components content especially total sulfur content reach standard-required.

Summary of the invention: the object of the invention is to, for high simultaneously high containing H containing organosulfur in oil and gas₂the situation of S, proposes a kind of high-efficient purification sweetening agent (Unitedly developed desulfur solvent is called for short UDS), is removing high density H₂s and CO₂time, efficiently removing the organic sulfides such as high concentration CO S and mercaptan, single stage method is removed to each acidic components the desired value of requirement.

Sweetening agent of the present invention and other solvent phase ratios, UDS sweetening agent is being processed the oil and gas of high sulfur compound, during the especially high oil and gas containing organic sulfide, shows more outstanding advantage.For the reliable exploitation of peracidity natural-gas field provides assurance, simplified removing process simultaneously, improved the economy of technique.

Main technical schemes of the present invention is: UDS sweetening agent is comprised of the water of the sulfur heterocyclic compound and 10～80% (wt) containing oxygen and/or nitrogen heterocyclic B, 0.1～30% (wt) containing oxygen and/or nitrogen heterocyclic A, 0.1～30% (wt) of the alcohol amine compound, 15～75% (wt) of weight percent 10～85% (wt).

Usually, alcohol amine compound of the present invention is primary amine, secondary amine compound, tertiary amine compound or two or more the mixture in them; The Optimum of alcohol amine compound is 10～70%.

Described compd A is monocycle, dicyclo or tricyclic compound, preferably single six-membered rings oxaza compound; The consumption of compd A is 25～65%.

Described compd B is for containing oxygen and/or nitrogen heterocyclic, preferably hexa-atomic nitrogenous unsaturated heterocyclic compound; The Optimum of compd B is 0.1～15%.

Described sulfur heterocyclic compound is five yuan or hexa-atomic sulfur heterocyclic compound; Sulfur heterocyclic compound Optimum is 0.1～15%.

Described peracidity oil and gas can be contain～20% (mol) H₂s ,～2000mg/Nm³organosulfur and/or～20% (mol) CO₂acid oil and gas; Described organosulfur is one or more the mixture in carbonylsulfide, thiomethyl alcohol, sulfur alcohol, propylmercaptan and other mercaptan or sulfide compound; The pressure of peracidity oil and gas can be at 0.1MPa to 8.5MPa.

UDS sweetening agent can replace single alcohol amine compound by the mixture of the alcohol amine compound with two or more, can reach the (H particularly of the unwanted component in Sweet natural gas₂s and CO₂) more effective removing, expanded the adaptability to raw material simultaneously.

UDS sweetening agent can significantly increase the adaptability of solvent to each sulfide in unstripped gas by adding containing oxygen and/or nitrogen heterocyclic A, improves total sulfur removal rate, significantly reduces total sulfur content in cleaning of off-gas.

By adding in UDS sweetening agent containing oxygen and/or nitrogen heterocyclic B, can significantly increase the assimilating activity of solvent to sulfide, improve desulfurization rate.

Due to adding of sulfur heterocyclic compound, UDS sweetening agent is stronger to the binding ability of sulfide, while being used as the purifying solvent of high sulfide content oil and gas, can show more superior desulfurization performance.

UDS sweetening agent and common hydramine solvent phase ratio, there is the advantages such as desulfurization degree is high, Heat stability is good, low, the anti-degradation capability of regeneration energy consumption is strong, race damage is low, bubble less, corrodibility is little, for high sulfur content, the particularly purification of high organic sulfur content oil and gas, there is obvious advantage.

Accompanying drawing explanation: accompanying drawing 1 is embodiment of the present invention embodiment block flowsheet sketch.

Embodiment: the present invention is described in detail below in conjunction with embodiment and accompanying drawing.

When the present embodiment is used UDS sweetening agent to purify peracidity oil and gas, can implement according to the mode of accompanying drawing 1:

Peracidity oil and gas contacts with absorption liquid anti-phase in absorption tower, the purified gas removing after acidic components is discharged from tower top, the rich solution that has absorbed acidic components is from entering the hydrocarbon that rich solution flash tank flashes off dissolving out at the bottom of tower, after the rich solution after flash distillation and the heat exchange of regeneration lean solution, enters regenerator column desorption and regeneration.Separate the sour gas of sucking-off and discharged by regeneration overhead, the lean solution after regeneration is discharged at the bottom of by tower, through with rich solution heat exchange and cooling after get back to absorption tower and recycle.Compare with there being the technique of COS hydrolysis reactor, this technique is simple economy more obviously.

Embodiment one

In peracidity oil and gas, contain organosulfur 999.1mg/Nm³, H₂s15.11% (mol), CO₂8.96% (mol).By the flow process shown in Fig. 1, carry out absorption experiment, the formula that UDS sweetening agent adopts is: five yuan of sulfur heterocyclic compounds of the hexa-atomic nitrogenous unsaturated heterocyclic compound, 2% (wt) of the diethanolamine, 2% (wt) of the single six-membered rings oxaza compound of 26% (wt), the monoethanolamine, 3% (wt) of 3% (wt), the water of 59% (wt), all the other are N methyldiethanol amine.16 ℃ of absorption temperature, absorption pressure 2 * 10⁵pa, raw gas flow 55.3L/h, absorption liquid internal circulating load 0.42L/h.Absorb and process organosulfur 16.2mg/Nm in after purification gas³, H₂s4mg/Nm³, CO₂<0.1% (mol).Organic sulfur removal rate is 98.77%.

Embodiment two

In peracidity oil and gas, contain organosulfur 999.1mg/Nm³, H₂s15.11% (mol), CO₂8.96% (mol).By the flow process shown in Fig. 1, carry out absorption experiment, the formula that UDS sweetening agent adopts is: five yuan of sulfur heterocyclic compounds of the hexa-atomic nitrogenous unsaturated heterocyclic compound, 3% (wt) of the diethanolamine, 3% (wt) of the single six-membered rings oxaza compound of 42% (wt), the monoethanolamine, 5% (wt) of 5% (wt), the water of 35% (wt), all the other are N methyldiethanol amine.18 ℃ of absorption temperature, absorption pressure 2 * 10⁵pa, raw gas flow 20.9L/h, absorption liquid internal circulating load 0.54L/h.Absorb and process organosulfur 19.6mg/Nm in after purification gas³, H₂s1.5mg/Nm³, CO₂<0.1% (mol).Organic sulfur removal rate is 98.51%.

Embodiment three

In peracidity oil and gas, contain organosulfur 1110mg/Nm³, H₂s16.8% (mol), CO₂8.8% (mol).By the flow process shown in Fig. 1, carry out absorption experiment, the formula that UDS sweetening agent adopts is: five yuan of sulfur heterocyclic compounds of the hexa-atomic nitrogenous unsaturated heterocyclic compound, 3% (wt) of the diethanolamine, 2% (wt) of the single six-membered rings oxaza compound of 32% (wt), the monoethanolamine, 4% (wt) of 4% (wt), the water of 50% (wt), all the other are N methyldiethanol amine.40 ℃ of absorption temperature, absorption pressure 15 * 10⁵pa, raw gas flow 135L/h, absorption liquid internal circulating load 0.8L/h.Absorb and process organosulfur 81.6mg/Nm in after purification gas³, H₂s<0.5mg/Nm³, CO₂<0.1% (mol).Organic sulfur removal rate is 94.49%.

Embodiment four

In peracidity oil and gas, contain organosulfur 1258.6mg/Nm³, CO₂8.3% (mol).By the flow process shown in Fig. 1, carry out absorption experiment, the formula that UDS sweetening agent adopts is: five yuan of sulfur heterocyclic compounds of the hexa-atomic nitrogenous unsaturated heterocyclic compound, 3% (wt) of the diethanolamine, 2% (wt) of the single six-membered rings oxaza compound of 32% (wt), the monoethanolamine, 4% (wt) of 4% (wt), the water of 50% (wt), all the other are N methyldiethanol amine.33 ℃ of absorption temperature, absorption pressure 10.5 * 10⁵pa, raw gas flow 100L/h, absorption liquid internal circulating load 0.8L/h.Absorb and process organosulfur 70.8mg/Nm in after purification gas³, CO₂<0.1% (mol).Organic sulfur removal rate is 94.84%.

Embodiment five

In peracidity oil and gas, contain organosulfur 1100mg/Nm³, H₂s17.2% (mol), CO₂8.5% (mol).By the flow process shown in Fig. 1, carry out absorption experiment, the formula that UDS sweetening agent adopts is: five yuan of sulfur heterocyclic compounds of the hexa-atomic nitrogenous unsaturated heterocyclic compound, 3% (wt) of the diethanolamine, 2% (wt) of the single six-membered rings oxaza compound of 32% (wt), the monoethanolamine, 4% (wt) of 4% (wt), the water of 50% (wt), all the other are N methyldiethanol amine.40 ℃ of absorption temperature, absorption pressure 83 * 10⁵pa, raw gas flow 400L/h, absorption liquid internal circulating load 5L/h.Absorb and process organosulfur 38.1mg/Nm in after purification gas³, H₂s46.6mg/Nm³, CO₂<0.2% (mol).Organic sulfur removal rate is 97.43%.

Embodiment six

In peracidity oil and gas, contain organosulfur 999.1mg/Nm³, H₂s15.11% (mol), CO₂8.96% (mol).By the flow process shown in Fig. 1, carry out absorption experiment, the formula that UDS sweetening agent adopts is: five yuan of sulfur heterocyclic compounds of the hexa-atomic nitrogenous unsaturated heterocyclic compound, 2% (wt) of the diethanolamine, 2% (wt) of the single six-membered rings oxaza compound of 22% (wt), the monoethanolamine, 4% (wt) of 4% (wt), the water of 64% (wt), all the other are N methyldiethanol amine.19 ℃ of absorption temperature, absorption pressure 2 * 10⁵pa, raw gas flow 52.2L/h, absorption liquid internal circulating load 0.45L/h.Absorb and process organosulfur 355.5mg/Nm in after purification gas³, H₂s52mg/Nm³, CO₂<0.1% (mol).Organic sulfur removal rate is 72.96%.

Comparative example one

In peracidity oil and gas, contain organosulfur 999.1mg/Nm³, H₂s15.11% (mol), CO₂8.96% (mol).By the flow process shown in Fig. 1, carry out absorption experiment, sweetening agent adopts the MDEA of 65% (wt), 17 ℃ of absorption temperature, absorption pressure 2 * 10⁵pa, raw gas flow 55.3L/h, absorption liquid internal circulating load 0.42L/h.Absorb and process after purification gas containing organosulfur 603.3mg/Nm³, H₂s145mg/Nm³, CO₂0.65% (mol).Organic sulfur removal rate is 54.11%.

Comparative example two

In peracidity oil and gas, contain organosulfur 1110mg/Nm³, H₂s15.3% (mol), CO₂8.4% (mol).By the flow process shown in Fig. 1, carry out absorption experiment, sweetening agent adopts the MDEA of 50% (wt), 40 ℃ of absorption temperature, absorption pressure 15 * 10⁵pa, raw gas flow 135L/h, absorption liquid internal circulating load 0.8L/h.Absorb and process after purification gas containing organosulfur 432.8mg/Nm³, H₂s<0.5mg/Nm³, CO₂0.3% (mol).Organic sulfur removal rate is 69.91%.

Comparative example three

In peracidity oil and gas, contain organosulfur 1100mg/Nm³, H₂s16.3% (mol), CO₂8.7% (mol).By the flow process shown in Fig. 1, carry out absorption experiment, sweetening agent adopts the MDEA of 50% (wt).40 ℃ of absorption temperature, absorption pressure 83 * 10⁵pa, raw gas flow 500L/h, absorption liquid internal circulating load 5L/h.Absorb and process organosulfur 536.2mg/Nm in after purification gas³, H₂s116.1mg/Nm³, CO₂0.6% (mol).Organic sulfur removal rate is 63.18%.

Claims (3)

Translated fromChinese

1.一种高效净化脱硫剂的用途，所述的脱硫剂组成为： 26%(wt)的六元单环氧氮杂环化合物、3%(wt)的单乙醇胺、3%(wt)的二乙醇胺、2%(wt)的六元含氮不饱和杂环化合物、2%(wt)的五元含硫杂环化合物、59%(wt)的水，其余为N-甲基二乙醇胺；其特征在于将其用于从高酸性石油天然气中脱除酸性组分，所述的高酸性石油天然气是含有~20%(mol) H₂S、~2000 mg/Nm³有机硫和/或~20%(mol) CO₂的酸性石油天然气；所述有机硫是羰基硫、甲硫醇、乙硫醇、丙硫醇以及其他硫醇或硫醚化合物中的一种或几种的混合物；所述的高酸性石油天然气的压力在0.1 MPa至8.5 MPa。1. the purposes of a kind of high-efficiency purification desulfurizer, described desulfurizer consists of: the monoethanolamine of 26% (wt) six-membered epoxy nitrogen heterocycle compound, 3% (wt), the monoethanolamine of 3% (wt) Diethanolamine, 2% (wt) six-membered nitrogen-containing unsaturated heterocyclic compound, 2% (wt) five-membered sulfur-containing heterocyclic compound, 59% (wt) water, and the rest are N-methyldiethanolamine; It is characterized in that it is used to remove acid components from highly acidic oil and gas containing ~20% (mol) H₂ S, ~2000 mg/Nm³ organic sulfur and/or ~ 20% (mol)_CO2 sour oil and natural gas; the organic sulfur is one or more mixtures of carbonyl sulfide, methyl mercaptan, ethanethiol, propylene mercaptan and other mercaptan or thioether compounds; The pressure of the above-mentioned highly acidic oil and gas is between 0.1 MPa and 8.5 MPa.2.一种高效净化脱硫剂的用途，所述的脱硫剂组成为：42%(wt)的六元单环氧氮杂环化合物、5%(wt)的单乙醇胺、5%(wt)的二乙醇胺、3%(wt)的六元含氮不饱和杂环化合物、3%(wt)的五元含硫杂环化合物、35%(wt)的水，其余为N-甲基二乙醇胺；其特征在于将其用于从高酸性石油天然气中脱除酸性组分，所述的高酸性石油天然气是含有~20%(mol) H₂S、~2000 mg/Nm³有机硫和/或~20%(mol) CO₂的酸性石油天然气；所述有机硫是羰基硫、甲硫醇、乙硫醇、丙硫醇以及其他硫醇或硫醚化合物中的一种或几种的混合物；所述的高酸性石油天然气的压力在0.1 MPa至8.5 MPa。2. the purposes of a kind of high-efficiency purification desulfurizer, described desulfurizer consists of: the monoethanolamine of 42% (wt) six-unit epoxy nitrogen heterocyclic compound, 5% (wt) monoethanolamine, 5% (wt) Diethanolamine, 3% (wt) six-membered nitrogen-containing unsaturated heterocyclic compound, 3% (wt) five-membered sulfur-containing heterocyclic compound, 35% (wt) water, and the rest are N-methyldiethanolamine; It is characterized in that it is used to remove acid components from highly acidic oil and gas containing ~20% (mol) H₂ S, ~2000 mg/Nm³ organic sulfur and/or ~ 20% (mol)_CO2 sour oil and natural gas; the organic sulfur is one or more mixtures of carbonyl sulfide, methyl mercaptan, ethanethiol, propylene mercaptan and other mercaptan or thioether compounds; The pressure of the above-mentioned highly acidic oil and gas is between 0.1 MPa and 8.5 MPa.3.一种高效净化脱硫剂的用途，所述的脱硫剂组成为：32%(wt)的六元单环氧氮杂环化合物、4%(wt)的单乙醇胺、4%(wt)的二乙醇胺、2%(wt)的六元含氮不饱和杂环化合物、3%(wt)的五元含硫杂环化合物、50%(wt)的水，其余为N-甲基二乙醇胺；其特征在于将其用于从高酸性石油天然气中脱除酸性组分，所述的高酸性石油天然气是含有~20%(mol) H₂S、~2000 mg/Nm³有机硫和/或~20%(mol) CO₂的酸性石油天然气；所述有机硫是羰基硫、甲硫醇、乙硫醇、丙硫醇以及其他硫醇或硫醚化合物中的一种或几种的混合物；所述的高酸性石油天然气的压力在0.1 MPa至8.5 MPa。3. A kind of purposes of efficient purifying desulfurizer, described desulfurizer consists of: 32% (wt) of six-membered epoxy nitrogen heterocyclic compound, 4% (wt) of monoethanolamine, 4% (wt) of Diethanolamine, 2% (wt) six-membered nitrogen-containing unsaturated heterocyclic compound, 3% (wt) five-membered sulfur-containing heterocyclic compound, 50% (wt) water, and the rest are N-methyldiethanolamine; It is characterized in that it is used to remove acid components from highly acidic oil and gas containing ~20% (mol) H₂ S, ~2000 mg/Nm³ organic sulfur and/or ~ 20% (mol)_CO2 sour oil and natural gas; the organic sulfur is one or more mixtures of carbonyl sulfide, methyl mercaptan, ethanethiol, propylene mercaptan and other mercaptan or thioether compounds; The pressure of the above-mentioned highly acidic oil and gas is between 0.1 MPa and 8.5 MPa.

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