阅读说明：本技术 生物脱硫污泥系统快速启动与调控方法 (Quick starting and regulating method for biological desulfurization sludge system ) 是由 杨帆 吴伟林 官峻 陈剑锋 张鑫 王志明 于 2021-10-12 设计创作，主要内容包括：本发明涉及生物脱硫污泥系统快速启动与调控方法,使用带有自加热以及保温功能的污泥培养容器,可以对污泥的温度进行调控及保持,充分保证污泥中微生物的培养环境,促进硫氧化菌群发育繁殖。通过间隔均匀投加脱硫菌剂的方式,保证容器内的微生物结构稳定,使相关菌群在污泥体系中占据主导位置,加快污泥培育速度,最终达到快速驯化和优选硫氧化细菌的目的。(The invention relates to a quick start and regulation method of a biological desulfurization sludge system, which uses a sludge culture container with self-heating and heat preservation functions to regulate and maintain the temperature of sludge, fully ensures the culture environment of microorganisms in the sludge and promotes the development and propagation of sulfur oxidizing bacteria. By means of uniformly adding the desulfurization microbial inoculum at intervals, the structure stability of microorganisms in the container is ensured, related flora occupies a leading position in a sludge system, the sludge cultivation speed is accelerated, and the aims of quickly domesticating and preferably selecting sulfur-oxidizing bacteria are finally fulfilled.)

1. The quick starting and regulating method of the biological desulfurization sludge system is characterized by comprising the following steps: the method comprises the following steps:

step 1, connecting activated sludge into a reactor, and adjusting the internal temperature of the reactor;

step 2, preparing reactor inlet water containing sludge microorganism cultures, pumping the reactor inlet water into a reactor through a peristaltic pump, and maintaining the hydraulic retention time for 20-26 hours;

step 3, uniformly feeding desulfurization bacterial powder into the reactor at intervals for 4-6 days;

and 4, detecting the generation amount of the elemental sulfur and the flora in the reactor, and determining the state of the sludge in the reactor.

2. The method for rapidly starting and regulating the biological desulfurization sludge system according to claim 1, characterized in that: the reactor is heated by resistance wires.

3. The method for rapidly starting and regulating the biological desulfurization sludge system according to claim 2, characterized in that: in the step 1, the temperature in the reactor is kept between 29 and 31 ℃.

4. The method for rapidly starting and regulating the biological desulfurization sludge system according to claim 1, characterized in that: the activated sludge is granular sludge with the particle size of 4-6 mm.

5. The method for rapidly starting and regulating the biological desulfurization sludge system according to claim 4, characterized in that: the ratio of VSS to SS of the activated sludge is as follows: VSS/SS is 0.6-0.7.

6. The method for rapidly starting and regulating the biological desulfurization sludge system according to claim 4, characterized in that: the volume of the activated sludge is 60-80% of the effective working capacity of the reactor.

7. The method for rapidly starting and regulating the biological desulfurization sludge system according to claim 1, characterized in that: the sludge microbial culture contained 1500mg/L NaHCO₃127.5mg/L of NO₃-N, 200mg/L sulfideAnd trace elements.

8. The method for rapidly starting and regulating the biological desulfurization sludge system according to claim 7, characterized in that: the trace elements comprise MgSO₄、MnSO₄·H₂O、NaCl、FeSO₄·7H₂O、CaCl₂·2H₂O、CoCl₂·6H₂O、ZnCl₂、CuSO₄·5H₂O、AlK(SO₄)₂·12H₂O、H₃BO₃、Na₂MoO₄、NiCl₂·6H₂O、Na₂WO₄·2H₂O。

Technical Field

The invention belongs to the technical field of biological desulfurization, and particularly relates to a quick starting and regulating method of a biological desulfurization sludge system.

Background

With the continuous development of social economy, the demand for petroleum resources is increasing day by day. However, in the development process of the petroleum field, under the influence of various factors, the petroleum pipeline is easy to corrode, and the sustainable development of the petroleum industry, particularly the corrosion problem of hydrogen sulfide, is greatly hindered. The oilfield associated gas produced with the crude oil generally contains part of water vapor, and some of the oilfield associated gas also contains a considerable amount of acid gases such as hydrogen sulfide, carbon dioxide and the like. The water vapor in associated gas not only reduces the transportation capacity of the pipeline and the calorific value of the gas, but also may cause the water vapor to be separated out from the natural gas to form liquid water, ice or solid hydrate of the natural gas when the transportation pressure and the environment are changed, thereby increasing the pressure drop of the pipeline and even plugging the pipeline. When the associated gas contains acid gas, the corrosion of pipelines and equipment by hydrogen sulfide and carbon dioxide is accelerated. The consequences can be quite severe if mishandled, resulting in hydrogen sulfide leakage.

The optimal application fields of gas biological desulfurization and sulfur recovery are large-scale desulfurization of natural gas, coke oven gas, chemical tail gas and the like, and can replace complex iron and wet oxidation desulfurization processes. Compared with a wet chemical oxidation method, biological desulfurization has obvious advantages in indexes such as sulfur, sulfur capacity and the like, but higher requirements are put forward on indexes such as sulfur conversion rate, alkali consumption, volume load and the like of biological desulfurization, and technical breakthroughs in aspects such as sulfur oxidizing bacteria, a biological desulfurization reactor, a process control strategy and the like need to be made.

Sulfur oxidizing bacteria are a generic term for a class of microorganisms having the ability to oxidize sulfur. Certain sulfur bacteria, autotrophic denitrifying sulfur oxidizing bacteria, are capable of oxidizing sulfur compounds (nitrates, nitrites) to elemental sulfur using the nitrogen-based compounds as electron acceptors, while simultaneously reducing the nitrates or nitrites to nitrogen, thereby gaining energy for growth and metabolism in the process. The major sulfur oxidizing bacteria include T.dentrifi cans, Thiobacillus dentrifi cans, Thiobacillus versutus, Thiobacilla pantropha and P.dentrifi cans. The more obvious the functional flora needs to be domesticated and preferentially desulfurized in the biological desulfurization reactor, the better the desulfurization effect and the stronger the impact resistance of the functional flora. Because various mutual assistance and competition mechanisms exist in the activated sludge, such as the fact that denitrifying bacteria and sulfate reducing bacteria compete for organic substrates and the like, and sulfur oxidizing bacteria need to be domesticated and optimized rapidly in industrial application, the method takes sulfur oxidizing bacteria enrichment as a target, and rapidly starts a biological desulfurization sludge system by controlling the operation conditions of a reactor, so that sulfide removal and elemental sulfur output are realized.

Disclosure of Invention

The invention aims to provide a quick starting and regulating method of a biological desulfurization sludge system, and solve the problem of slow starting of the biological desulfurization sludge system.

The technical scheme adopted by the invention for solving the technical problems is as follows: the quick starting and regulating method of the biological desulfurization sludge system comprises the following steps:

step 1, connecting activated sludge into a reactor, and adjusting the internal temperature of the reactor;

step 2, preparing reactor inlet water containing sludge microorganism cultures, pumping the reactor inlet water into a reactor through a peristaltic pump, and maintaining the hydraulic retention time for 20-26 hours;

step 3, uniformly feeding desulfurization bacterial powder into the reactor at intervals for 4-6 days;

and 4, detecting the generation amount of the elemental sulfur and the flora in the reactor, and determining the state of the sludge in the reactor.

Preferably, the reactor is heated by using a resistance wire.

Preferably, in the step 1, the temperature in the reactor is maintained at 29 ℃ to 31 ℃.

Preferably, the activated sludge is granular sludge with the grain diameter of 4-6 mm.

Preferably, the ratio of VSS to SS of the activated sludge is: VSS/SS is 0.6-0.7.

Preferably, the volume of the activated sludge is 60% to 80% of the effective working capacity of the reactor.

Preferably, the sludge is micro-grownThe culture broth contained 1500mg/L NaHCO₃127.5mg/L of NO₃N, 200mg/L sulfide and trace elements.

Preferably, the trace element comprises MgSO₄、MnSO₄·H₂O、NaCl、FeSO₄·7H₂O、CaCl₂·2H₂O、CoCl₂·6H₂O、ZnCl₂、CuSO₄·5H₂O、AlK(SO₄)₂·12H₂O、H₃BO₃、Na₂MoO₄、NiCl₂·6H₂O、Na₂WO₄·2H₂O。

The invention has the following beneficial effects: the sludge culture container with self-heating and heat preservation functions is used, the temperature of the sludge can be regulated and maintained, the culture environment of microorganisms in the sludge is fully ensured, and the development and propagation of sulfur oxidizing bacteria groups are promoted. By means of uniformly adding the desulfurization microbial inoculum at intervals, the density of desulfurization flora in the container is ensured, related flora occupies a leading position in a sludge system, the sludge cultivation speed is increased, and the purpose of increasing the starting speed of the desulfurization sludge system is finally achieved.

Drawings

FIG. 1 is a schematic diagram of a reactor configuration;

FIG. 2 is a graph showing the effect of removing sulfides;

FIG. 3 is a structural diagram of a bacterial community.

Detailed Description

The specific structure of the reactor is shown in figure 1, the reactor is composed of organic glass, the working volume is 3L, the diameter is 6cm, and polyurethane biological sponge filler is filled in the reactor.

Example 1

(1) Inoculating granular activated sludge into a reactor, wherein the average grain diameter of the sludge is 5mm, and VSS/SS is 0.68, and heating by using a resistance wire to keep the temperature in the reactor at 30 +/-1 DEG C

(2) The feed water contained 1500mg/L NaHCO₃127.5mg/L of NO₃N, 200mg/L sulfide and trace elements. The trace elements comprise MgSO₄ 3g/L、MnSO₄·H₂O 0.5g/L、NaCl 1g/L、FeSO₄·7H₂O 0.1g/L、CaCl₂·2H₂O 0.1g/L、CoCl₂·6H₂O 0.1g/L、ZnCl₂ 0.13g/L、H₃BO₃ 0.01g/L、Na₂MoO₄0.025g/L、NiCl₂·6H₂O 0.024g/L、Na₂WO₄·2H₂O 0.025g/L、CuSO₄·5H₂O 0.01g/L、AlK(SO₄)₂·12H₂O0.01 g/L, pumped into the reactor by a peristaltic pump, and retained for 24 hours by waterpower.

(3) 0.1L of solid bacterial powder is added every 5 days for 5 times, and then the microbial inoculum is not added.

(4) The concentration of sulphide in the feed water to the reactor was maintained at 200 mg/L. As can be seen from FIG. 2, the amount of elemental sulfur produced was 151mg/L in the first day of the operation of the reactor, and the amount of elemental sulfur produced was 144.4mg/L to 154.1mg/L in 40 days. The reactor started under the method has no obvious startup period, and the generation amount of elemental sulfur has no obvious fluctuation during the operation. The removal rate of sulfide by the reactor microorganisms started up is kept at a relatively high level.

As can be seen from FIG. 3, the main dominant genera in the initial sludge are the genera Azoarcus (49.2%), Pseudomonas (5.3%), Thauera (13.2%), Arcobacter (4.4%), whereas the genera Thiobacillus are hardly detectable. On day 5, Thiobacillus and Unlasified Betaproteobacteria are the absolute dominant genera, accounting for 58.6% and 26.9%, respectively. The relative abundance of each species of facultative and heterotrophic bacteria is less than 2%. On day 20, the predominant species in the reactor at this time were still Thiobacillus and Unlasified beta proteobacteria. The overall relative abundance of the remaining bacteria becomes smaller. After 5 times of continuous addition of the microbial inoculum, namely after 25 days, the microbial inoculum is not added. The OTU sequence of Arcobacter was barely detectable on days 5 and 20, while the relative abundance of Arcobacter increased to 10.3% on day 40. The relative abundance of Thiobacillus species decreased from 56% to 45.2% at day 40, and the relative abundance of Unlasified Betaproteobacteria was 33.0%. This demonstrates that the process allows start-up desulfurization bacteria to quickly dominate the microbial system in the reactor.

Comparative example 1

(1) Inoculating granular activated sludge into a reactor, wherein the average grain diameter of the sludge is 5mm, and VSS/SS is 0.68, and heating by using a resistance wire to keep the temperature in the reactor at 30 +/-1 DEG C

(2) The feed water contained 1500mg/L NaHCO₃127.5mg/L of NO₃N, 200mg/L sulfide and trace elements. The trace elements comprise MgSO₄ 3g/L、MnSO₄·H₂O 0.5g/L、NaCl 1g/L、FeSO₄·7H₂O 0.1g/L、CaCl₂·2H₂O 0.1g/L、CoCl₂·6H₂O 0.1g/L、ZnCl₂ 0.13g/L、H₃BO₃ 0.01g/L、Na₂MoO₄0.025g/L、NiCl₂·6H₂O 0.024g/L、Na₂WO₄·2H₂O 0.025g/L、CuSO₄·5H₂O 0.01g/L、AlK(SO₄)₂·12H₂O0.01 g/L, pumped into the reactor by a peristaltic pump, and retained for 24 hours by waterpower.

(3) 0.5L of solid bacterial powder is added at one time, and then the solid bacterial powder is not added.

(4) The concentration of sulphide in the feed water was maintained at 200 mg/L. As can be seen from FIG. 2, the amount of elemental sulfur produced was 179.5mg/L on the first day of the operation of the reactor, and the rate of elemental sulfur production then gradually decreased to 123.6mg/L on the 40 th day.

As can be seen from FIG. 2, the relative abundance of Thiobacillus reached 75.4% to absolute dominance at day 5. Another dominant genus is Lutibacter, the relative abundance of which is 6.8%, and the only carbon source which can be utilized is maltose. In addition, the relative abundance of the genus Pseudomonas at this time was 4.8%. This suggests that heterotrophic and facultative bacteria are still required to participate in their internal balance, even in situations where autotrophic bacteria dominate the community structure. On day 20, the relative abundance of Thiobacillus decreased to 59%, while that of Unlasified beta proteobacteria increased to 14.7%. The microbial inoculum which may be added gradually runs off, and on the other hand, the Thiobacillus genus and the Unlasified beta proteobacteria may be in competition relationship. The relative abundance of the Lutibacter genus decreased to 0.8%, and the relative abundance of the Pseudomonas genus decreased to 1.6%. It is speculated that the Unlasified Betaproteobacteria may play a role in replacing heterotrophic or facultative bacteria in an autotrophic system. On day 40, the relative abundance of the uncalasied beta proteobacteria and Thiobacillus reached equilibrium, 36.7% and 35.2%, respectively. The relative abundance of Arcobacter is 3.6%.

Comparative example 2

(1) Inoculating granular activated sludge into a reactor, wherein the average grain diameter of the sludge is 5mm, and VSS/SS is 0.68, and heating by using a resistance wire to keep the temperature in the reactor at 30 +/-1 DEG C

(2) The feed water contained 1500mg/L NaHCO₃127.5mg/L of NO₃N, 200mg/L sulfide and trace elements. The trace elements comprise MgSO₄ 3g/L、MnSO₄·H₂O 0.5g/L、NaCl 1g/L、FeSO₄·7H₂O 0.1g/L、CaCl₂·2H₂O 0.1g/L、CoCl₂·6H₂O 0.1g/L、ZnCl₂ 0.13g/L、H₃BO₃ 0.01g/L、Na₂MoO₄0.025g/L、NiCl₂·6H₂O 0.024g/L、Na₂WO₄·2H₂O 0.025g/L、CuSO₄·5H₂O 0.01g/L、AlK(SO₄)₂·12H₂O0.01 g/L, pumped into the reactor by a peristaltic pump, and retained for 24 hours by waterpower.

(3) No microbial inoculum is added.

(4) Starting effect

The concentration of sulphide in the feed water was maintained at 200 mg/L. It can be seen from FIG. 2 that the rate of elemental sulfur formation in the reactor was gradually increased until day 30 to reach a relatively steady state.

As can be seen from FIG. 3, only the Azoarcus remained in the original colony structure at day 5, and the yield decreased from 49.2% to 15.6%. Thiobacillus genus is raised to 27.4%. Also, the relative abundance increased from 5.3% to 19.4% for Pseudomonas and from 4.4% to 19.1% for Arcobacter. Pseudomonas and Arcobacter are heterotrophic or facultative bacteria that are capable of utilizing both organic and inorganic carbon sources. The reason why heterotrophic or facultative bacteria are able to survive in an autotrophic environment may be due to the organic substrates produced by the autotrophic bacteria Thiobacillus upon substantial survival, which provide organic substrates for both bacteria. After 20 days of culture, the genus Azoarcus has been barely detected, while the genera Pseudomonas and Arcobacter continue to decline, both in relative abundance of less than 2%. The relative abundance of Thiobacillus now continues to rise from 27.4% to 57.6%. At this time the relative abundance of another genus rapidly increased, and the OTU of this genus bacterium was almost absent in the initial sludge and the sludge on day 5. Due to taxonomic limitations and current lack of understanding, this bacterium is only classified in Unlasified beta proteobacteria. The relative abundance of this genus increased to 22.0% at day 20. Also the relative abundance of this genus increased to 35.1% at day 40. Whereas the relative abundance of Thiobacillus decreased to 41.2%. The genus Arcobacter became the dominant genus again at day 40, although its OTU was barely detectable at day 20. And combining the concentration of the elementary sulfur in the effluent (126 mg/L-132.9 mg/L) at the 35 th to 40 th days, which shows that the microbial community structure in the reactor reaches the final stable structure at the 40 th day.

Therefore, in the container in example 1 in which the bacterial powder is added at intervals, both the elemental sulfur generation amount and the microbial community stability are superior to those of other operation modes, and it is seen that the rapid start method of the biological desulfurization sludge system in the invention can enable the biological desulfurization sludge system to have no obvious start period, and the elemental sulfur generation amount fluctuation is small during the desulfurization operation, and the microbial community structure is stable.

In summary, although the present invention has been described with reference to the preferred embodiments, the above-described preferred embodiments are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, therefore, the scope of the present invention shall be determined by the appended claims.